1, 8-diazaspiro [4.5] decane-2, 4-dione derivatives useful as pesticides

ABSTRACT

A compound of the formula (1) wherein the substituents are as defined in claim  1 , are useful as a pesticides.

This application is a 371 of International Application No.PCT/EP2011/058182 filed May 19, 2011, which claims priority to EP10164512.5 filed May 31, 2010, the contents of which are incorporatedherein by reference.

The present invention relates to new 3-substituted N-alkyl amidesubstituted spiroheterocyclic pyrrolidine dione derivatives, toprocesses for preparing them, to pesticidal, in particular insecticidal,acaricidal, molluscicidal and nematicidal compositions comprising themand to methods of using them to combat and control pests such as insect,acarine, mollusc and nematode pests.

N-alkyl amide substituted spiroheterocyclic pyrrolidine dionederivatives are disclosed for example in WO 10/066,780. Further,spiroheterocyclic pyrrolidine dione derivatives are known, for example,from WO 10/115,780.

It has now surprisingly been found that certain novel 3-substitutedN-alkyl amide substituted spiroheterocyclic pyrrolidine dionederivatives have good insecticidal properties.

The present invention therefore provides compounds of formula I

wherein

X, Y and Z independently of each other are C₁₋₄alkyl, C₃₋₆cycloalkyl,C₁₋₄alkoxy, halogen, phenyl or phenyl substituted by C₁₋₄alkyl,C₁₋₄haloalkyl, halogen or cyano;

m and n, independently of each other, are 0, 1, 2 or 3 and m+n is 0, 1,2 or 3;

G is halogen or nitro;

R is hydrogen, C₁₋₆alkyl, C₁₋₆cyanoalkyl, C₂₋₆alkenyl, C₂₋₆haloalkenyl,C₃₋₆alkynyl, benzyl, C₁₋₄alkoxy(C₁₋₄)alkyl, orC₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl; and

A is C₁₋₆alkyl, C₃₋₆cycloalkyl, C₃₋₆cycloalkyl(C₁₋₄)alkyl, orC₃₋₆cycloalkyl(C₁₋₄)alkyl where in the cycloalkyl moiety a methylenegroup is replaced by O, S or NR₀, where R₀ is C₁₋₆alkyl or C₁₋₆alkoxy,or A is C₂₋₆alkenyl, C₂₋₆haloalkenyl, C₃₋₆alkynyl, C₁₋₆cyanoalkyl,benzyl, C₁₋₄alkoxy(C₁₋₄)alkyl, C₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl,oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, C₁₋₆alkylcarbonyl,C₁₋₆alkoxycarbonyl, C₃₋₆cycloalkylcarbonyl, N-di(C₁₋₆alkyl)carbamoyl,benzoyl, C₁₋₆alkylsulfonyl, phenylsulfonyl, C₁₋₄alkylthio(C₁₋₄)alkyl,C₁₋₄alkylsulfinyl(C₁₋₄)alkyl or C₁₋₄alkylsulfonyl(C₁₋₄)alkyl;

or an agrochemically acceptable salt or an N-oxide thereof.

In the compounds of the formula I, each alkyl moiety either alone or aspart of a larger group is a straight or branched chain and is, forexample, methyl, ethyl, n-propyl, n-butyl, iso-propyl, sec-butyl,iso-butyl, tert-butyl, n-pentyl, iso-pentyl and n-hexyl.

Alkoxy groups preferably have a preferred chain length of from 1 to 4carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy,i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy. Such groupscan be part of a larger group such as alkoxyalkyl and alkoxyalkoxyalkyl.Alkoxyalkyl groups preferably have a chain length of 1 to 4 carbonatoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl,ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl orisopropoxymethyl.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, forexample cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. In theserings, a methylene group can be replaced by an oxygen and/or sulphuratom, which leads, for example, to oxetanyl, tetrahydrofuranyl,tetrahydropyranyl, furanyl, tetrahydro-thiofuranyl andtetrahydro-thiopyranyl rings.

Phenyl, also as part of a substituent such as benzyl, may besubstituted, preferably by alkyl, haloalkyl, halogen or cyano groups. Inthis case, the substituents can be in ortho, meta and/or para position.The preferred substituent positions are the ortho and para positions tothe ring attachment point.

The latentiating groups G are selected to allow its removal by one or acombination of biochemical, chemical or physical processes to affordcompounds of formula I where G is hydrogen before, during or followingapplication to the treated area or plants. Examples of these processesinclude enzymatic cleavage, chemical hydrolysis and photoloysis.Compounds bearing such groups G may offer certain advantages, such asimproved penetration of the cuticula of the plants treated, increasedtolerance of crops, improved compatibility or stability in formulatedmixtures containing other herbicides, herbicide safeners, plant growthregulators, fungicides or insecticides, or reduced leaching in soils.

The compounds of formula I may exist in different geometric or opticalisomers or different tautomeric forms. One or more centres of chiralitymay be present, in which case compounds of the formula I may be presentas pure enantiomers, mixtures of enantiomers, pure diastereomers ormixtures of diastereomers. Centres of tautomerisation may be present.This invention covers all such isomers and tautomers and mixturesthereof in all proportions as well as isotopic forms such as deuteratedcompounds.

The invention relates also to the agriculturally acceptable salts whichthe compounds of formula I are able to form with transition metal,alkali metal and alkaline earth metal bases, amines, quaternary ammoniumbases or tertiary sulfonium bases.

Among the transition metal, alkali metal and alkaline earth metal saltformers, special mention should be made of the hydroxides of copper,iron, lithium, sodium, potassium, magnesium and calcium, and preferablythe hydroxides, bicarbonates and carbonates of sodium and potassium.

Examples of amines suitable for ammonium salt formation include ammoniaas well as primary, secondary and tertiary C₁-C₁₈alkylamines,C₁-C₄hydroxyalkylamines and C₂-C₄alkoxyalkyl-amines, for examplemethylamine, ethylamine, n-propylamine, propylamine, the four butylamineisomers, n-amylamine, i-amylamine, hexylamine, heptylamine, octylamine,nonylamine, decylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,methylhexylamine, methylnonylamine, methylpentadecylamine,methyloctadecylamine, ethylbutylamine, ethylheptylamine,ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine,diethylamine, di-n-propylamine, di-1-propylamine, di-n-butylamine,di-n-amylamine, di-1-amylamine, dihexylamine, diheptylamine,dioctylamine, ethanolamine, n-propanolamine, i-propanolamine,N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine,allylamine, n-but-2-enylamine, n-pent-2-enylamine,2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-enylamine,propylenediamine, trimethylamine, triethylamine, tri-n-propylamine,tri-1-opropylamine, tri-n-butylamine, tri-1-butylamine,tri-sec-butylamine, tri-n-amylamine, methoxyethylamine andethoxyethylamine; heterocyclic amines, for example pyridine, quinoline,isoquinoline, morpholine, piperidine, pyrrolidine, indoline,quinuclidine and azepine; primary arylamines, for example anilines,methoxyanilines, ethoxyanilines, o-, m- and p-toluidines,phenylenediamines, benzidines, naphthylamines and o-, m- andp-chloroanilines; but especially triethylamine, i-propylamine anddi-1-propylamine.

Preferred quaternary ammonium bases suitable for salt formationcorrespond, for example, to the formula [N(R_(a) R_(b) R_(c) R_(d))]OH,wherein R_(a), R_(b), R_(c) and R_(d) are each independently of theothers hydrogen or C₁-C₄alkyl. Further suitable tetraalkylammonium baseswith other anions can be obtained, for example, by anion exchangereactions.

Preferred tertiary sulfonium bases suitable for salt formationcorrespond, for example, to the formula [SR_(e)R_(f)R_(g)]OH, whereinR_(e), R_(f) and R_(g) are each independently of the others C₁-C₄ alkyl.Trimethylsulfonium hydroxide is especially preferred. Suitable sulfoniumbases may be obtained from the reaction of thioethers, in particulardialkylsulfides, with alkylhalides, followed by conversion to a suitablebase, for example a hydroxide, by anion exchange reactions.

The compounds of formula I according to the invention also includehydrates which may be formed during the salt formation.

The preferred values of G, R, A, X, Y, Z, m and n in the compounds offormula I in any combination thereof are set out below.

Preferably G is fluoro, chloro, bromo, iodo or nitro. It is preferredthat G is fluoro, chloro, bromo or nitro and even more preferably G isfluoro, chloro or nitro.

Preferably R is hydrogen, C₁₋₆alkyl, C₁₋₆haloalkyl, C₁₋₆cyanoalkyl,C₂-C₆alkenyl, C₂₋₆haloalkenyl, C₃-C₆alkynyl, benzyl,C₁₋₄alkoxy(C₁₋₄)alkyl or C₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl, inparticular hydrogen, methyl, ethyl, n-propyl, isopropyl, cyanomethyl,trifluoromethyl, 2,2,2-trifluoroethyl, allyl, 3,3-dichloroallyl,propargyl, benzyl, methoxymethyl, ethoxymethyl, methoxyethyl ormethoxyethoxymethyl.

Preferably A is C₁₋₆alkyl, C₁₋₆haloalkyl, C₃₋₆cycloalkyl,C₃₋₆cycloalkyl(C₁₋₄)alkyl, or C₃₋₆cycloalkyl(C₁₋₄)alkyl where in thecycloalkyl moiety a methylene group is replaced by O, S or NR₀, where R₀is C₁₋₆alkyl or C₁₋₆alkoxy, or A is C₂₋₆alkenyl, C₃₋₆alkynyl, benzyl,C₁₋₄alkoxy(C₁₋₄)alkyl, C₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl orC₁₋₄alkylthio(C₁₋₄)alkyl, in particular methyl, ethyl, isopropyl,trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl,cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,oxetan-3-ylmethyl, tetrahydrofuran-2-ylmethyl,tetrahydropyran-2-ylmethyl, tetrahydrofuran-3-ylmethyl,tetrahydropyran-3-ylmethyl, tetrahydropyran-4-ylmethyl, allyl,propargyl, benzyl, methoxymethyl, ethoxymethyl, methoxyethyl,methoxypropyl, methoxyethoxymethyl, methoxymethoxyethyl, oxetan-3-yl,tetrahydropyran-4-yl or methylthioethyl.

Preferably X is C₁-C₄alkyl, C₃-C₆cycloalkyl, C₁-C₄alkoxy or halogen.

More preferably X is methyl, ethyl, cyclopropyl, methoxy, fluoro, bromoor chloro.

Preferably Y and Z, independently of each other, are C₁-C₄alkyl,C₃-C₆cycloalkyl, C₁-C₄alkoxy, halogen, phenyl, phenyl substituted byC₁-C₄alkyl or halo-substituted phenyl and m+n is 1, 2 or 3 and inparticular m+n is 1 or 2.

More preferably Y and Z, independently of each other, are methyl, ethyl,cyclopropyl, methoxy, fluoro, bromo or chloro, phenyl orhalo-substituted phenyl (in particular fluorophenyl or chlorophenyl andespecially 4-chlorophenyl or 4-fluorophenyl) and m+n is 1, 2 or 3 and inparticular m+n is 1 or 2.

Yet more preferably Y and Z are each independently methyl, ethyl,cyclopropyl, methoxy, fluoro, bromo or chloro and m+n is 1, 2 or 3, inparticular, m+n is 1 or 2.

In one preferred group of compounds of the formula (I), R is hydrogen,methyl, ethyl, isopropyl, cyanomethyl, 2,2,2-trifluoroethyl, allyl,propargyl, benzyl, methoxymethyl, ethoxymethyl, methoxyethyl ormethoxyethoxymethyl, A is methyl, ethyl, isopropyl, trifluoromethyl,2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl,cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,oxetan-3-ylmethyl, tetrahydrofuran-2-ylmethyl,tetrahydropyran-2-ylmethyl, tetrahydrofuran-3-ylmethyl,tetrahydropyran-3-ylmethyl, tetrahydropyran-4-ylmethyl, allyl,propargyl, benzyl, methoxymethyl, ethoxymethyl, methoxyethyl,methoxypropyl, methoxyethoxymethyl, methoxymethoxyethyl, oxetanyl-3-yl,tetrahydropyran-4-yl or methylthioethyl, X is methyl, ethyl,cyclopropyl, methoxy, fluoro, bromo or chloro, Y and Z, independently ofeach other, are methyl, ethyl, cyclopropyl, methoxy, fluoro, chloro,bromo, phenyl or phenyl substituted by halogen or C₁-C₂alkyl, G has themeanings assigned to it above and m+n is 1, 2 or 3.

In another preferred group of compounds of the formula (I), R is methyl,ethyl, 2,2,2-trifluoroethyl, allyl, propargyl, benzyl, methoxymethyl ormethoxyethyl, A is methyl, ethyl, isopropyl, 2,2,2-trifluoroethyl,cyclopropyl, cyclopentyl, cyclopropylmethyl, tetrahydrofuran-2-ylmethyl,tetrahydrofuran-3-ylmethyl, tetrahydropyran-4-ylmethyl, allyl,propargyl, benzyl, methoxymethyl, methoxyethyl, methoxypropyl,methoxyethoxymethyl, methoxymethoxyethyl or methylthioethyl, X ismethyl, ethyl, cyclopropyl, methoxy, fluoro, bromo or chloro, Y and Z,independently of each other, are methyl, ethyl, cyclopropyl, methoxy,fluoro, chloro, bromo, phenyl or phenyl substituted by halogen orC₁-C₂alkyl, G has the meanings assigned to it above and m+n is 1, 2 or3.

In yet another preferred group of compounds of the formula (I), R ismethyl, ethyl, 2,2,2-trifluoroethyl, benzyl, methoxymethyl ormethoxyethyl, A is methyl, ethyl, isopropyl, 2,2,2-trifluoroethyl,cyclopropyl, cyclopentyl, cyclopropylmethyl, tetrahydrofuran-2-ylmethyl,tetrahydrofuran-3-ylmethyl, tetrahydropyran-4-ylmethyl, allyl,propargyl, benzyl, methoxymethyl, methoxyethyl, methoxypropyl,methoxyethoxymethyl, methoxymethoxyethyl or methylthioethyl, X ismethyl, ethyl, cyclopropyl, methoxy, fluoro, bromo or chloro, Y and Z,independently of each other, are methyl, ethyl, cyclopropyl, methoxy,fluoro, chloro, bromo, phenyl or phenyl substituted by halogen orC₁-C₂alkyl, G is fluoro, chloro or nitro and m+n is 1-3.

In yet another preferred group of compounds of the formula (I), R ismethyl or benzyl, A is methyl, cyclopropylmethyl,tetrahydrofuran-2-ylmethyl or methoxyethyl, X is methyl or chloro, Y andZ, independently of each other, are methyl, ethyl, methoxy, bromo,phenyl or phenyl substituted by chloro, G is chloro or nitro and m+n is1-3.

The invention covers also salts of the compounds of the formula I withamines, alkali metal and alkaline earth metal bases or quaternaryammonium bases.

Among the alkali metal and alkaline earth metal hydroxides as saltformers, special mention should be made of the hydroxides of lithium,sodium, potassium, magnesium and calcium, but especially the hydroxidesof sodium and potassium. The compounds of formula I according to theinvention also include hydrates which may be formed during the saltformation.

Examples of amines suitable for ammonium salt formation include ammoniaas well as primary, secondary and tertiary C₁-C₁₈alkylamines,C₁-C₄hydroxyalkylamines and C₂-C₄alkoxyalkylamines, for examplemethylamine, ethylamine, n-propylamine, isopropylamine, the fourbutylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,methylhexylamine, methylnonylamine, methylpentadecylamine,methyloctadecylamine, ethylbutylamine, ethylheptylamine,ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine,diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine,di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine,dioctylamine, ethanolamine, n-propanolamine, isopropanolamine,N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine,allylamine, n-but-2-enylamine, n-pent-2-enylamine,2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-enylamine,propylenediamine, trimethylamine, triethylamine, tri-n-propylamine,triisopropylamine, tri-n-butylamine, triisobutylamine,tri-sec-butylamine, tri-n-amylamine, methoxyethylamine andethoxyethylamine; heterocyclic amines, for example pyridine, quinoline,isoquinoline, morpholine, piperidine, pyrrolidine, indoline,quinuclidine and azepine; primary arylamines, for example anilines,methoxyanilines, ethoxyanilines, o-, m- and p-toluidines,phenylenediamines, benzidines, naphthylamines and o-, m- andp-chloroanilines; but especially triethylamine, isopropylamine anddiisopropylamine.

Preferred quaternary ammonium bases suitable for salt formationcorrespond, for example, to the formula [N(R_(a) R_(b) R_(c) R_(d))]OHwherein R_(a), R_(b), R_(c) and R_(d) are each independently of theothers C₁-C₄alkyl. Further suitable tetraalkylammonium bases with otheranions can be obtained, for example, by anion exchange reactions.

The compounds of the invention may be made by a variety of methods. Forexample, the compounds of formula I, wherein the substituents have themeanings assigned to them above, can be prepared by means of processesknown per se, e.g. by treating compounds of formula II with ahalogenating or nitrating agent:

Compounds of the formula I, in which X, Y, Z, m, n, R and A are asdefined above and wherein G is a halogen, may be prepared by knownprocedures as described, for example, in JP 2000086628. Typically,compounds of formula II, in which X, Y, Z, m, n, R and A are as definedabove, are treated with halogenating agents in the presence of asolvent, optionally in the presence of a base, and, if appropriate, inthe presence of a free-radical initiator. Suitable halogenating agentsare, for example, chlorine, sulfuryl chloride, sulfuryl bromide, thionylchloride, thionyl chloride, imides such as, for example,N-chlorosuccinimide or N-bromosuccinimide, chlorosulfonic acid,hypochlorites such as, for example, tert-butyl hypochlorite or sodiumhypochlorite, electrophilic fluorinating agents such as, for example,Selectfluor [1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octanebis(tetrafluoroborate)], Accufluor[1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2.2.2]octanebis(tetrafluoroborate)], Florinate FP-T 500 [N-fluoropyridiniumtrifluoromethanesulfonate] or NFSI [N-fluorodibenzenesulfonimide].Suitable solvents for this reaction are selected to be compatible withthe reagents and include, for example, carbon tetrachloride, chloroform,dichloromethane, dichloroethane, acetonitrile, ethyl acetate, benzene,toluene, chlorobenzene, tetrahydrofuran or dioxane. Suitablefree-radical initiators are, for example, benzoyl peroxide, AlBN[α,α′-azodiisobutyronitrile] or the like. Suitable bases for thisreaction are selected to be compatible with the reagents and include,for example, alkali metal or alkaline earth metal carbonates, acetatesor hydroxides, such as sodium hydrogen carbonate, potassium carbonate,sodium acetate or lithium hydroxide. Compounds of the formula I, inwhich X, Y, Z, m, n, R and A are as defined above and wherein Grepresents nitro, may be prepared by reacting compounds of formula II,in which X, Y, Z, m, n, R and A are as defined above, with nitratingagents, such as, for example, fuming nitric acid or nitrating acidmixtures in the presence of a solvent, preferably chloroform,dichloromethane, dichloroethane, chlorobenzene or acetic acid, underconditions known to a person skilled in the art (see for example:Nitrobarbituric Acid, W. W. Hartman, O. E. Sheppard, Organic Syntheses12, 1932).

Depending on the nature of the substituents, compounds of formula II mayexist in different isomeric forms, in particular in different tautomericforms:

This invention covers all such isomers and tautomers and mixturesthereof in all proportions.

Compounds of formula III, in which X, Y, Z, m, n, A and G are as definedabove,

can be obtained by catalytic hydrogenation of compounds of formula I, inwhich X, Y, Z, m, n, A and G are as defined above and in which R isrepresented by a benzyl group.

Compounds of formula I, in which X, Y, Z, m, n, R, A and G are asdefined above, can be obtained by treating compounds of formula III, inwhich X, Y, Z, m, n, A and G are as defined above, with an alkylatingagent R-Q, wherein R represents the alkyl group to be incorporated and Qrepresents a nucleofuge, in the presence of at least one equivalent of abase, and optionally in the presence of a suitable solvent.

Compounds of formula II may be prepared via the cyclisation of compoundsof formula IV,

wherein R₁₄ is C₁₋₆alkyl, preferably in the presence of base, andoptionally in the presence of a suitable solvent, by known methods inanalogy to those described, for example, in WO 09/049,851.

Compounds of formula IV, wherein R₁₄ is as defined above and wherein Ais C₁₋₆alkyl, C₁₋₆haloalkyl, C₃₋₆cycloalkyl, C₃₋₆cycloalkyl(C₁₋₄)alkyl,or C₃₋₆cycloalkyl(C₁₋₄)alkyl where in the cycloalkyl moiety a methylenegroup is replaced by O, S or NR₀, where R₀ is C₁₋₆alkyl or C₁₋₆alkoxy,or A is C₂₋₆alkenyl, C₂₋₆haloalkenyl, C₃₋₆alkynyl, C₁₋₆cyanoalkyl,benzyl, C₁₋₄alkoxy(C₁₋₄)alkyl, C₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl,oxetanyl, tetrahydrofuranyl, tetrahydropyranyl orC₁₋₄alkylthio(C₁₋₄)alkyl, may be prepared by treatment of a compound offormula XVI with an alkylating agent of formula A-Y″, wherein A is thealkyl group to be incorporated and Y″ is a halogen (especially bromineor iodine), sulfonate (especially mesylate or tosylate) or a sulfate,preferably in the presence of a base, under known conditions.

Compounds of formula IV, in which R₁₄ is as defined above and in which Arepresents C₁₋₆alkylcarbonyl, C₁₋₆alkoxycarbonyl,C₃₋₆cycloalkylcarbonyl, N-di(C₁₋₆alkyl)carbamoyl, benzoyl,C₁₋₆alkylsulfonyl or phenylsulfonyl, can be obtained by treatingcompounds of formula XVI with an acylating or sulfonylating agent A-Q,wherein A is the acyl or sulfonyl group to be incorporated and Qrepresents a nucleofuge, in the presence of at least one equivalent of abase, under known conditions, described for example by S. M. B. Fraga etal., Eur. J. Org. Chem. (2004), (8), 1750-1760.

Compounds of formula IV, wherein R₁₄ is as defined above and wherein Ais C₁₋₆alkylcarbonyl, C₁₋₆alkoxycarbonyl, C₃₋₆cycloalkylcarbonyl orN-di(C₁₋₆alkyl)carbamoyl, may also be prepared by treating compounds offormula XVI with phosgene or a phosgene equivalent, optionally in thepresence of a solvent such as toluene or ethyl acetate, and a base andreacting the resultant chloroformate, or equivalent, with an alcohol oran amine, under known conditions.

Compounds of formula IV, wherein R₁₄ is as defined above and wherein Ais C₁₋₆alkylsulfonyl or phenylsulfonyl, may be prepared by reaction ofcompounds of formula XVI with an alkyl or phenyl sulfonyl halide,preferably in the presence of at least one equivalent of base, underknown conditions.

Suitable conditions are the same as described above for the conversionof compounds of formula II to compounds of formula I. Compounds offormula XVI are known and have been described, for example, in WO09/049,851.

Compounds of formula II, wherein A is C₁₋₆alkyl, C₁₋₆haloalkyl,C₃₋₆cycloalkyl, C₃₋₆cycloalkyl(C₁₋₄)alkyl, or C₃₋₆cycloalkyl(C₁₋₄)alkylwhere in the cycloalkyl moiety a methylene group is replaced by O, S orNR₀, where R₀ is C₁₋₆alkyl or C₁₋₆alkoxy, or A is C₂₋₆alkenyl,C₂₋₆haloalkenyl, C₃₋₆alkynyl, C₁₋₆cyanoalkyl, benzyl,C₁₋₄alkoxy(C₁₋₄)alkyl, C₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl, oxetanyl,tetrahydrofuranyl, tetrahydropyranyl or C₁₋₄alkylthio(C₁₋₄)alkyl, mayalso be prepared in a two-step one-pot process involving

-   (i) amide N-alkylation of compounds of formula XVI with an agent    A-Y″, where A is the alkyl group to be incorporated and wherein Y″    represents a nucleofuge as defined above, in the presence of at    least one equivalent of a base, and-   (ii) cyclisation of the intermediate compounds of formula IV,    preferably in the presence of additional base, at least one more    equivalent, and optionally in the presence of a suitable solvent, by    methods described above.

R₁₄ is typically C₁-C₆alkyl. The base for steps (i) and (ii) may be thesame or different.

Compounds of formula IV may be prepared by reacting N-substituted aminoacid derivatives of formula V with phenylacetyl halides of formula VI,preferably in the presence of a base in a suitable solvent, by knownmethods in analogy to those described, for example, in WO 09/049,851.The base may be inorganic such as an alkali metal carbonate or hydroxideor a metal hydride, or an organic base such as a tertiary amine or metalalkoxide. Examples of suitable inorganic bases include sodium carbonate,sodium or potassium hydroxide, sodium hydride, and suitable organicbases include trialkylamines such as trimethylamine and triethylamine,pyridines or other amine bases such as 1,4-diazobicyclo[2.2.2]octane and1,8-diazabicyclo[5.4.0]undec-7-ene. Preferred bases includetriethylamine and pyridine. Suitable solvents for this reaction areselected to be compatible with the reagents and include ethers such astetrahydrofuran and 1,2-dimethoxyethane and halogenated solvents such asdichloromethane and chloroform. Certain bases, such as pyridine andtriethylamine, may be employed successfully as both base and solvent.

Phenylacetyl halides of formula VI, wherein Hal is Cl or Br, are knowncompounds or can be prepared by known methods, described for example inWO 09/049,851.

N-substituted amino acid esters of the formula V, wherein R₁₄ isC₁-C₆alkyl, may be prepared by reacting N-substituted amino nitriles ofthe formula VII with an alcohol of the formula R₁₄OH, preferably in thepresence of a strong acid (especially sulfuric acid or hydrochloricacid), under known conditions.

N-substituted amino acid esters of the formula V, wherein R₁₄ isC₁-C₆alkyl, can also be prepared by known methods from N-substitutedamino acids of formula VIII. Esterification of VIII with an alcohol ofthe formula R₁₄OH under thionyl chloride activation is a typical examplefor the preparation of esters V, as described for example inWO09/049851, but other known esterification methods may also be applied,like for example treatment of a compound of the formula VIII with analcohol of the formula R₁₄OH under acidic conditions (typically H₂SO₄ orHCl). For the particular situation where R₁₄ is methyl, a compound ofthe formula VIII may also be treated with diazomethane ortrimethylsilyldiazomethane, or with acetyl chloride in methanol. Thecompounds VIII, VII and V can be reacted and/or isolated as free aminesor amine salts (eg a hydrohalide salt, more specifically a hydrochlorideor hydrobromide salt, or any other equivalent salt).

N-substituted amino acids of formula VIII can themselves be prepared byknown methods, typically under hydrolysis conditions usually eitheracidic or basic, from N-substituted amino nitriles of the formula VII. Arepresentative example for the nitrile hydrolysis into its correspondingcarboxylic acid functionality under aqueous H₂SO₄ or HCl conditions maybe found, for example, in E. F. G. Duynstee et al., Recueil Tray. Chim.Pays-Bas 84, 1442-1451, (1965) or in B. Wang et al., Eur. J. Org. Chem.(2008), (2), 350-355.

Ultimately, N-substituted amino acids of formula VIII can be preparedfrom ketones of formula X by means of a Strecker-type synthesis viaN-substituted amino nitriles of formula VII. The transformation ketone Xto N-substituted amino nitriles VII (Strecker reaction) is a welldescribed one-pot three components coupling involving, besides ketonesX, hydrogen cyanide HCN or various alkali cyanides (eg KCN, NaCN, etc.)in buffered aqueous media or trimethylsilyl cyanide TMSCN, optionally inpresence of a catalytic amount of a Lewis acid, for example ZnI₂, and aN-substituted amine of the formula H₂N-A either as free amine or aminesalt (eg a hydrohalide salt, more specifically a hydrochloride orhydrobromide salt, or any other equivalent salt of the amine H₂N-A). Anappropriate source of cyanide (eg HCN) may also be added to a preformedketimine (or iminium salt) between ketone X and the N-substituted amineH₂N-A, or a salt thereof. A summary on the scope of the Streckerreaction may be found, for example, in L. Kürti, B. Czakó, ‘StrategicApplications of Named Reactions in Organic Synthesis’, Elsevier AcademicPress, 2005, pp. 446-447 and 690-691. Typical reaction conditions forthe Strecker reaction may be found also, for example, in M. M. Mehrotraet al., J. Med. Chem. (2004), 47, 2037-2061, or B. J. Mavunkel et al.,J. Med. Chem. (1996), 39, 3169-3173, or P. L. Feldman et al., J. Org.Chem. (1990), 55, 4207-4209, or in J. L. Marco et al., Tetrahedron(1999), 55, 7625-7644. Alternatively, amino acids of formula VIII canalso be prepared from ketones of formula X by means of a Bucherer Bergsreaction, described for example in Th. Wieland et al., Methoden Org.Chem. (Houben-Weyl) (1959), Bd. XI/2, 305-306, via N1-substitutedhydantoins of formula IX. The transformation ketone X into hydantoin IXcan be achieved, for example, in analogy to L. Tang et al., Heterocycles(2007), 74, 999-1008. N-1 substituted hydantoins IX may also beconveniently prepared from N-substituted amino nitriles VII by treatmentwith an alkali cyanate (eg potassium cyanate KOCN), followed by acidicaqueous hydrolysis in analogy to, for example, G. M. Carrera et al., J.Heterocyclic Chem. (1992), 29, 847-850 or I. M. Bell et al., Bioorg.Med. Chem. Lett. (2006), 16, 6165-6169. Yet another option for thecyclisation of N-substituted amino nitriles VII into spirohydantoins IXis the reaction with chlorosulfonyl isocyanate CISO₂NCO in, for example,dichloromethane, followed by acidic aqueous hydrolysis in analogy to,for example, P. L. Feldman et al., J. Org. Chem. (1990), 55, 4207-4209or M. W. Rowbottom, Bioorg. Med. Chem. Lett. (2007), 17, 2171-2178.

N-substituted amino acids of formula VIII can be prepared by knownmethods, typically under thermal hydrolysis conditions usually eitheracidic or basic, from N1-substituted hydantoins IX. A representativeexample for the hydantoin hydrolysis into the corresponding amino acidfunctionality under aqueous NaOH conditions may be found, for example,in P. L. Feldman et al., J. Org. Chem. (1990), 55, 4207-4209.

The compounds VIII, VII and V can be reacted and/or isolated as freeamines or amine salts (eg a hydrohalide salt, more specifically ahydrochloride or hydrobromide salt, or any other equivalent salt).

Compounds of formula X, where R is C₁₋₆alkyl, C₂-C₆alkenyl,C₃-C₆alkynyl, C₁₋₆cyanoalkyl, benzyl, C₁₋₄alkoxy(C₁₋₄)alkyl orC₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl are known or can be obtained, forexample, according to Major and Dursch, Journal of Organic Chemistry(1961), 26, 1867-74.

Alternatively, compounds of formula IV may be prepared by subjectingderivatives of formula XI to alcoholysis with R₁₄OH, preferably instrong acidic media (especially sulfuric acid or hydrochloric acid) byknown methods in analogy to those described, for example, in WO09/049,851.

Compounds of formula XI may be themselves prepared by reactingN-substituted amino nitriles of formula VII with phenylacetyl halides offormula VI, preferably in the presence of base in a suitable solvent, byknown methods in analogy to those described, for example, in WO09/049,851. The base may be inorganic such as an alkali metal carbonateor hydroxide or a metal hydride, or an organic base such as a tertiaryamine or metal alkoxide. Examples of suitable inorganic bases includesodium carbonate, sodium or potassium hydroxide, sodium hydride, andsuitable organic bases include trialkylamines such as trimethylamine andtriethylamine, pyridines or other amine bases such as1,4-diazobicyclo[2.2.2]octane and 1,8-diazabicyclo[5.4.0]undec-7-ene.Preferred bases include triethylamine and pyridine. Suitable solventsfor this reaction are selected to be compatible with the reagents andinclude ethers such as tetrahydrofuran and 1,2-dimethoxyethane andhalogenated solvents such as dichloromethane and chloroform. Certainbases, such as pyridine and triethylamine, may be employed successfullyas both base and solvent.

Compounds of formula XI may also be prepared by treatment of a compoundof formula XVII with an alkylating agent of formula A-Y″, wherein A isthe alkyl group to be incorporated and Y″ is a halogen (especiallybromine or iodine), sulfonate (especially mesylate or tosylate) or asulfate, or with an acylating or sulfonylating agent A-Q, wherein A isthe acyl or sulfonyl group to be incorporated and Q represents anucleofuge, preferably in the presence of a base, under knownconditions.

Suitable conditions are the same as described above for the conversionof compounds of formula XVI to compounds of formula IV. Compounds offormula XVII are known and have been described, for example, in WO09/049,851.

Compounds of formula II may also be prepared by reacting nitrilecompounds of formula XI with R₁₄OH in a strong acidic media (especiallysulfuric acid or hydrochloric acid), optionally in presence of asolvent, preferably at higher temperature, for example between 50-150°C., followed by hydrolysis conditions, for example by pouring the crudereaction mixture on ice, in a direct cyclisation sequence.

A further process for the preparation of compounds of formula IIinvolves catalytic hydrogenation of compounds of formula XIV having anenol benzyl ether functionality, in which the benzyl group might beoptionally substituted with T, wherein T is for example 4-methoxy or3,4-dimethoxy. Treatment of XIV with hydrogen (1-100 bars pressure) andcatalytic amounts of palladium (for example palladium on carbon 1-30 wt.%) in solvents like methanol or tetrahydrofuran, optionally furthercontaining water or acids like HCl, at 0-100° C. are typical reactionconditions for the hydrogenolytic debenzylation. A representativeprocedure can be found, for example, according to Schobert et al.,Organic & Biomolecular Chemistry 2004, 2, 3524-3529. Other mild reactionconditions to remove the benzyl group make use of triethylsilane and acatalytic amount of palladium(II) acetate in presence of a baseaccording, for example, to Paintner et al., Synlett 2003, 627-30.

Compounds of formula XIV may be prepared by treatment of a compound offormula XIII with an alkylating agent of formula A-Y″, wherein A is thealkyl group to be incorporated and Y″ is a halogen (especially bromineor iodine), sulfonate (especially mesylate or tosylate) or a sulfate,preferably in the presence of a base, under known conditions.

Compounds of formula XIII may be prepared by treatment of a compound offormula XII with a benzyl halide, which may be optionally substituted byT, wherein T is defined as above, in presence of a base, under knownconditions, for example in analogy to R. Labruere et al., Synthesis(2006), (24), 4163-4166 or Y. Bourdreux et al., Tetrahedron (2008),64(37), 8930-8937.

Suitable reaction conditions for the transformations XII to XIII andXIII to XIV are, for example, the same as described above for theconversion of compounds of formula II to compounds of formula I.Compounds of formula XII and XIII are known and have been described, forexample, in WO 09/049,851.

Yet another process for the preparation of compounds of formula IIinvolves treatment of compounds of formula XII with a base, at least twoequivalents, in the presence of a suitable solvent and at an appropriatetemperature to generate an intermediate dianion of formula XV, which isfurther treated with an alkylating agent of formula A-Y″, wherein A isthe alkyl group to be incorporated and Y″ is a halogen (especiallybromine or iodine), sulfonate (especially mesylate or tosylate) or asulfate, under known conditions.

Compounds of the formula I, wherein X, Y or Z is phenyl or phenylsubstituted by C₁₋₄alkyl, C₁₋₄haloalkyl, halogen or cyano, may beprepared by reacting a corresponding halogen precursor of the formulaId, wherein Hal is chlorine, bromine, iodine or a pseudohalogen such asC₁₋₄haloalkylsulfonate, especially triflate, and wherein G is as definedabove or is hydrogen, with an appropriate organometallic phenyl speciesof the formula XVIII, wherein T_(A) is C₁₋₄alkyl, C₁₋₄haloalkyl, halogenor cyano and M is for example B, Sn, Si, Mg or Zn holding furtherligands and/or substituents, by means of a transition metal-catalyzedreaction. The organometallic species of the formula XVIII is for examplean aryl boronic acid T_(A)-Phenyl-B(OH)₂, or a suitable salt or esterthereof, which will react with a compound of the formula Id underpalladium- or nickel-catalyzed conditions, such as for example theSuzuki-Miyaura conditions. A variety of metals, catalysts and ligandsmay be used in this reaction type. Reaction conditions and catalyticsystems for such a transformation have been described, for example, inWO08/071,405.

One person skilled in the art will recognize that the polarity at thetwo reacting centers in this cross-coupling process may be reversed.Compounds of the formula I, wherein X, Y or Z is phenyl or phenylsubstituted by C₁₋₄alkyl, C₁₋₄haloalkyl, halogen or cyano, may be alsoprepared by reacting a corresponding organometallic species of theformula Ie, wherein M is for example B, Sn, Si, Mg or Zn holding furtherligands and/or substituents, and wherein G is as defined above or ishydrogen, with an aryl halide of the formula XIX, wherein Hal ischlorine, bromine, iodine or a pseudohalogen such asC₁₋₄haloalkylsulfonate, especially triflate, by means of a transitionmetal-catalyzed reaction and under similar conditions as describedabove.

The sulfur oxidation state of compounds of the formula I, II, III, IV,XI and XIV, and of intermediates of the formula V, VII, VIII and IX,wherein A is incorporating such a S atom, like for example when A isC₁₋₄alkylthio(C₁₋₄)alkyl, may be easily adapted from the sulfideoxidation state into the sulfoxide or sulfone level by means of anoxidation reaction involving reagents such as, for example,m-chloroperbenzoic acid (MCPBA), oxone, sodium periodate, sodiumhypochlorite or tert-butyl hypochlorite amongst many others.

Certain compounds of formula II, III, IV, V, VII, VIII, IX, XI and XIV,and salts thereof, are novel and as such form a further aspect of theinvention.

The reactants can be reacted in the presence of a base. Examples ofsuitable bases are alkali metal or alkaline earth metal hydroxides,alkali metal or alkaline earth metal hydrides, alkali metal or alkalineearth metal amides, alkali metal or alkaline earth metal alkoxides,alkali metal or alkaline earth metal acetates, alkali metal or alkalineearth metal carbonates, alkali metal or alkaline earth metaldialkylamides or alkali metal or alkaline earth metal alkylsilylamides,alkylamines, alkylenediamines, free or N-alkylated saturated orunsaturated cycloalkylamines, basic heterocycles, ammonium hydroxidesand carbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. If thereaction is carried out in the presence of a base, bases which areemployed in excess, such as triethylamine, pyridine, N-methylmorpholineor N,N-diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between ambient temperature and approximately +80° C.

A compound I can be converted in a manner known per se into anothercompound I by replacing one or more substituents of the startingcompound I in the customary manner by (an)other substituent(s) accordingto the invention.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds I can be prepared in a manner known per se. Thus, forexample, acid addition salts of compounds I are obtained by treatmentwith a suitable acid or a suitable ion exchanger reagent and salts withbases are obtained by treatment with a suitable base or with a suitableion exchanger reagent.

Salts of compounds I can be converted in the customary manner into thefree compounds I, acid addition salts, for example, by treatment with asuitable basic compound or with a suitable ion exchanger reagent andsalts with bases, for example, by treatment with a suitable acid or witha suitable ion exchanger reagent.

Salts of compounds I can be converted in a manner known per se intoother salts of compounds I, acid addition salts, for example, into otheracid addition salts, for example by treatment of a salt of inorganicacid such as hydrochloride with a suitable metal salt such as a sodium,barium or silver salt, of an acid, for example with silver acetate, in asuitable solvent in which an inorganic salt which forms, for examplesilver chloride, is insoluble and thus precipitates from the reactionmixture.

Depending on the procedure or the reaction conditions, the compounds I,which have salt-forming properties can be obtained in free form or inthe form of salts.

The compounds I and, where appropriate, the tautomers thereof, in eachcase in free form or in salt form, can be present in the form of one ofthe isomers which are possible or as a mixture of these, for example inthe form of pure isomers, such as antipodes and/or diastereomers, or asisomer mixtures, such as enantiomer mixtures, for example racemates,diastereomer mixtures or racemate mixtures, depending on the number,absolute and relative configuration of asymmetric carbon atoms whichoccur in the molecule and/or depending on the configuration ofnon-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds I, in free formor in salt form, which can be obtained depending on which startingmaterials and procedures have been chosen can be separated in a knownmanner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl celulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereose-lective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds I and, where appropriate, the tautomers thereof, in eachcase in free form or in salt form, can, if appropriate, also be obtainedin the form of hydrates and/or include other solvents, for example thosewhich may have been used for the crystallization of compounds which arepresent in solid form.

The compounds according to the following Tables 1 to 155 below can beprepared according to the methods described above. The examples whichfollow are intended to illustrate the invention and show preferredcompounds of formula I.

TABLE 1 This table discloses the 132 compounds T1.001 to T1.132 of theformula Ia: (Ia)

wherein R is CH₃, A is CH₃, G is chlorine and R_(a), R_(b), R_(c) andR_(d) are as defined below: No. R_(a) R_(b) R_(c) R_(d) T1.001 Br H H HT1.002 Cl H H H T1.003 CH₃ H H H T1.004 CH₂CH₃ H H H T1.005 OCH₃ H H HT1.006 Br Cl H H T1.007 Cl Br H H T1.008 Cl Cl H H T1.009 Cl CH₃ H HT1.010 CH₃ Cl H H T1.011 CH₃ CH₃ H H T1.012 Cl H Cl H T1.013 Cl H CH₃ HT1.014 Cl H CH₂CH₃ H T1.015 Cl H OCH₃ H T1.016 CH₃ H CH₃ H T1.017 CH₃ HCH₂CH₃ H T1.018 CH₃ H OCH₃ H T1.019 CH₂CH₃ H CH₂CH₃ H T1.020 CH₂CH₃ HOCH₃ H T1.021 OCH₃ H OCH₃ H T1.022 Br H H Cl T1.023 Br H H CH₃ T1.024 BrH H 4-Cl-C₆H₄ T1.025 Cl H H Cl T1.026 Cl H H CH₃ T1.027 Cl H H 4-Cl-C₆H₄T1.028 CH₃ H H Br T1.029 CH₃ H H Cl T1.030 CH₃ H H CH₃ T1.031 CH₃ H HC₆H₅ T1.032 CH₃ H H 4-Cl-C₆H₄ T1.033 CH₂CH₃ H H CH₃ T1.034 CH₂CH₃ H H4-Cl-C₆H₄ T1.035 OCH₃ H H CH₃ T1.036 OCH₃ H H 4-Cl-C₆H₄ T1.037 Cl H ClBr T1.038 CH₃ H CH₃ Br T1.039 CH₃ H CH₃ Cl T1.040 CH₃ H CH₃ 4-Cl-C₆H₄T1.041 Br Cl H CH₃ T1.042 Br CH₃ H CH₃ T1.043 Cl Cl H Cl T1.044 Cl Br HCH₃ T1.045 Cl Cl H CH₃ T1.046 Cl CH₃ H Cl T1.047 Cl CH₃ H CH₃ T1.048 CH₃Br H CH₃ T1.049 CH₃ Cl H CH₃ T1.050 CH₃ CH₃ H CH₃ T1.051 CH₃ CH₃ H4-Cl-C₆H₄ T1.052 Br Br CH₃ H T1.053 Br Cl CH₃ H T1.054 Br CH₃ Br HT1.055 Br CH₃ Cl H T1.056 Cl Br CH₃ H T1.057 Cl Cl Cl H T1.058 Cl Cl CH₃H T1.059 Cl CH₃ Cl H T1.060 Cl CH₃ CH₂CH₃ H T1.061 Cl CH₃ OCH₃ H T1.062Cl 4-Cl-C₆H₄ Cl H T1.063 Cl 4-Cl-C₆H₄ CH₃ H T1.064 Cl 4-Cl-C₆H₄ CH₂CH₃ HT1.065 Cl 4-Cl-C₆H₄ OCH₃ H T1.066 CH₃ Br CH₃ H T1.067 CH₃ Cl CH₃ HT1.068 CH₃ CH₃ Br H T1.069 CH₃ CH₃ Cl H T1.070 CH₃ CH₃ CH₃ H T1.071 CH₃CH₃ CH₂CH₃ H T1.072 CH₃ CH₃ OCH₃ H T1.073 CH₃ 4-Cl-C₆H₄ CH₃ H T1.074 CH₃4-Cl-C₆H₄ CH₂CH₃ H T1.075 CH₃ 4-Cl-C₆H₄ OCH₃ H T1.076 CH₂CH₃ Br Br HT1.077 CH₂CH₃ Br Cl H T1.078 CH₂CH₃ Br CH₃ H T1.079 CH₂CH₃ Br CH₂CH₃ HT1.080 CH₂CH₃ Br OCH₃ H T1.081 CH₂CH₃ Cl Br H T1.082 CH₂CH₃ Cl Cl HT1.083 CH₂CH₃ Cl CH₃ H T1.084 CH₂CH₃ Cl CH₂CH₃ H T1.085 CH₂CH₃ Cl OCH₃ HT1.086 CH₂CH₃ CH₃ Br H T1.087 CH₂CH₃ CH₃ Cl H T1.088 CH₂CH₃ CH₃ CH₂CH₃ HT1.089 CH₂CH₃ CH₃ OCH₃ H T1.090 CH₂CH₃ CH₂CH₃ CH₃ H T1.091 CH₂CH₃ CH₂CH₃CH₂CH₃ H T1.092 CH₂CH₃ 4-Cl-C₆H₄ Br H T1.093 CH₂CH₃ 4-Cl-C₆H₄ CH₂CH₃ HT1.094 CH₂CH₃ 4-Cl-C₆H₄ OCH₃ H T1.095 OCH₃ Br CH₃ H T1.096 OCH₃ Cl CH₃ HT1.097 OCH₃ CH₃ Br H T1.098 OCH₃ CH₃ Cl H T1.099 OCH₃ CH₃ OCH₃ H T1.100OCH₃ 4-Cl-C₆H₄ OCH₃ H T1.101 CH₃ CH₃ CH₃ F T1.102 CH₃ CH₃ CH₃ Cl T1.103CH₃ CH₃ CH₃ Br T1.104 CH₃ CH₃ CH₃ CH₃ T1.105 CH₃ CH₃ CH₃ 4-Cl-C₆H₄T1.106 Cl CH₃ CH₃ CH₃ T1.107 CH₃ Cl CH₃ CH₃ T1.108 CH₃ CH₃ Cl CH₃ T1.109CH₂CH₃ CH₃ CH₃ CH₃ T1.110 OCH₃ CH₃ CH₃ CH₃ T1.111 Cyclo-C3 CH₃ CH₃ CH₃T1.112 CH₃ CH₃ Cyclo-C3 H T1.113 CH₃ F H Br T1.114 CH₃ CH₃ H Br T1.115CH₂CH₃ CH₃ H CH₃ T1.116 OCH₃ CH₃ H CH₃ T1.117 Cyclo-C3 CH₃ H CH₃ T1.118CH₂CH₃ Cl H CH₃ T1.119 OCH₃ Cl H CH₃ T1.120 Cyclo-C3 Cl H CH₃ T1.121 ClH CH₃ CH₃ T1.122 CH₃ H CH₃ CH₃ T1.123 CH₂CH₃ H CH₃ CH₃ T1.124 OCH₃ H CH₃CH₃ T1.125 Cyclo-C3 H CH₃ CH₃ T1.126 F H Cl CH₃ T1.127 Cl H F CH₃ T1.128H CH₃ CH₃ CH₃ T1.129 Br CH₃ CH₃ CH₃ T1.130 CH₃ H Cl CH₃ T1.131 CH₃ H BrCH₃ T1.132 Br H CH₃ CH₃ Cyclo-C3 means cyclopropyl.

-   Table 2: This table discloses the 132 compounds T2.001 to T2.132 of    the formula Ia, wherein R is CH₃, A is CH₂CH₃, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 3: This table discloses the 132 compounds T3.001 to T3.132 of    the formula Ia, wherein R is CH₃, A is n-C₃H₇, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 4: This table discloses the 132 compounds T4.001 to T4.132 of    the formula Ia, wherein R is CH₃, A is i-C₃H₇, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 5: This table discloses the 132 compounds T5.001 to T5.132 of    the formula Ia, wherein R is CH₃, A is n-C₄H₉, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 6: This table discloses the 132 compounds T6.001 to T6.132 of    the formula Ia, wherein R is CH₃, A is i-C₄H₉, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 7: This table discloses the 132 compounds T7.001 to T7.132 of    the formula Ia, wherein R is CH₃, A is t-C₄H₉, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 8: This table discloses the 132 compounds T8.001 to T8.132 of    the formula Ia, wherein R is CH₃, A is cyclopropyl, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 9: This table discloses the 132 compounds T9.001 to T9.132 of    the formula Ia, wherein R is CH₃, A is cyclopentyl, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 10: This table discloses the 132 compounds T10.001 to T10.132    of the formula Ia, wherein R is CH₃, A is cyclohexyl, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 11: This table discloses the 132 compounds T11.001 to T11.132    of the formula Ia, wherein R is CH₃, A is 2,2-(CH₃)₂-propyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 12: This table discloses the 132 compounds T12.001 to T12.132    of the formula Ia, wherein R is CH₃, A is allyl, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 13: This table discloses the 132 compounds T13.001 to T13.132    of the formula Ia, wherein R is CH₃, A is CH₂—CH═C(CH₃)₂, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 14: This table discloses the 132 compounds T14.001 to T14.132    of the formula Ia, wherein R is CH₃, A is CH₂—CH═C(Cl)₂, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 15: This table discloses the 132 compounds T15.001 to T15.132    of the formula Ia, wherein R is CH₃, A is propargyl, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 16: This table discloses the 132 compounds T16.001 to T16.132    of the formula Ia, wherein R is CH₃, A is CH₂C≡CCH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 17: This table discloses the 132 compounds T17.001 to T17.132    of the formula Ia, wherein R is CH₃, A is CH₂-cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 18: This table discloses the 132 compounds T18.001 to T18.132    of the formula Ia, wherein R is CH₃, A is CH₂CN, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 19: This table discloses the 132 compounds T19.001 to T19.132    of the formula Ia, wherein R is CH₃, A is CH₂OCH₃, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 20: This table discloses the 132 compounds T20.001 to T20.132    of the formula Ia, wherein R is CH₃, A is CH₂OCH₂CH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 21: This table discloses the 132 compounds T21.001 to T21.132 ofthe formula Ia, wherein R is CH₃, A is CH₂CH₂OCH₃, G is chlorine andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

-   Table 22: This table discloses the 132 compounds T22.001 to T22.132    of the formula Ia, wherein R is CH₃, A is CH₂OCH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 23: This table discloses the 132 compounds T23.001 to T23.132    of the formula Ia, wherein R is CH₃, A is CH₂CH₂OCH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 24: This table discloses the 132 compounds T24.001 to T24.132    of the formula Ia, wherein R is CH₃, A is oxetan-3-yl, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 25: This table discloses the 132 compounds T25.001 to T25.132    of the formula Ia, wherein R is CH₃, A is tetrahydrofuran-2-yl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 26: This table discloses the 132 compounds T26.001 to T26.132    of the formula Ia, wherein R is CH₃, A is tetrahydrofuran-3-yl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 27: This table discloses the 132 compounds T27.001 to T27.132    of the formula Ia, wherein R is CH₃, A is tetrahydropyran-2-yl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 28: This table discloses the 132 compounds T28.001 to T28.132    of the formula Ia, wherein R is CH₃, A is tetrahydropyran-4-yl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 29: This table discloses the 132 compounds T29.001 to T29.132    of the formula Ia, wherein R is CH₃, A is CH₂CH₂F, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 30: This table discloses the 132 compounds T30.001 to T30.132    of the formula Ia, wherein R is CH₃, A is CH₂CHF₂, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 31: This table discloses the 132 compounds T31.001 to T31.132    of the formula Ia, wherein R is CH₃, A is CH₂CF₃, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 32: This table discloses the 132 compounds T32.001 to T32.132    of the formula Ia, wherein R is CH₃, A is benzyl, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 33: This table discloses the 132 compounds T33.001 to T33.132    of the formula Ia, wherein R is CH₃, A is C(O)—CH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 34: This table discloses the 132 compounds T34.001 to T34.132    of the formula Ia, wherein R is CH₃, A is C(O)—OCH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 35: This table discloses the 132 compounds T35.001 to T35.132    of the formula Ia, wherein R is CH₃, A is C(O)-cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 36: This table discloses the 132 compounds T36.001 to T36.132    of the formula Ia, wherein R is CH₃, A is C(O)—N(CH₃)₂, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 37: This table discloses the 132 compounds T37.001 to T37.132    of the formula Ia, wherein R is CH₃, A is C(O)—C₆H₅, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 38: This table discloses the 132 compounds T38.001 to T38.132    of the formula Ia, wherein R is CH₃, A is SO₂CH₃, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 39: This table discloses the 132 compounds T39.001 to T39.132    of the formula Ia, wherein R is CH₃, A is SO₂C₆H₅, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 40: This table discloses the 132 compounds T40.001 to T40.132    of the formula Ia, wherein R is hydrogen, A is CH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 41: This table discloses the 132 compounds T41.001 to T41.132    of the formula Ia, wherein R is hydrogen, A is CH₂CH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 42: This table discloses the 132 compounds T42.001 to T42.132    of the formula Ia, wherein R is hydrogen, A is i-C₃H₇, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 43: This table discloses the 132 compounds T43.001 to T43.132    of the formula Ia, wherein R is hydrogen, A is cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 44: This table discloses the 132 compounds T44.001 to T44.132    of the formula Ia, wherein R is hydrogen, A is CH₂-cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 45: This table discloses the 132 compounds T45.001 to T45.132    of the formula Ia, wherein R is hydrogen, A is CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 46: This table discloses the 132 compounds T46.001 to T46.132    of the formula Ia, wherein R is hydrogen, A is CH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 47: This table discloses the 132 compounds T47.001 to T47.132    of the formula Ia, wherein R is hydrogen, A is CH₂OCH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 48: This table discloses the 132 compounds T48.001 to T48.132    of the formula Ia, wherein R is hydrogen, A is CH₂CH₂OCH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 49: This table discloses the 132 compounds T49.001 to T49.132    of the formula Ia, wherein R is hydrogen, A is oxetan-3-yl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 50: This table discloses the 132 compounds T50.001 to T50.132    of the formula Ia, wherein R is hydrogen, A is CH₂CHF₂, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 51: This table discloses the 132 compounds T51.001 to T51.132    of the formula Ia, wherein R is hydrogen, A is CH₂CF₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 52: This table discloses the 132 compounds T52.001 to T52.132    of the formula Ia, wherein R is hydrogen, A is benzyl, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 53: This table discloses the 132 compounds T53.001 to T53.132    of the formula Ia, wherein R is CH₂CH₃, A is CH₃, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 54: This table discloses the 132 compounds T54.001 to T54.132    of the formula Ia, wherein R is CH₂CH₃, A is CH₂CH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 55: This table discloses the 132 compounds T55.001 to T55.132    of the formula Ia, wherein R is CH₂CH₃, A is i-C₃H₇, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 56: This table discloses the 132 compounds T56.001 to T56.132    of the formula Ia, wherein R is CH₂CH₃, A is cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 57: This table discloses the 132 compounds T57.001 to T57.132    of the formula Ia, wherein R is CH₂CH₃, A is CH₂-cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 58: This table discloses the 132 compounds T58.001 to T58.132    of the formula Ia, wherein R is CH₂CH₃, A is CH₂OCH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 59: This table discloses the 132 compounds T59.001 to T59.132    of the formula Ia, wherein R is CH₂CH₃, A is CH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 60: This table discloses the 132 compounds T60.001 to T60.132    of the formula Ia, wherein R is CH₂CH₃, A is CH₂OCH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 61: This table discloses the 132 compounds T61.001 to T61.132    of the formula Ia, wherein R is CH₂CH₃, A is CH₂CH₂OCH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 62: This table discloses the 132 compounds T62.001 to T62.132    of the formula Ia, wherein R is CH₂CH₃, A is oxetan-3-yl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 63: This table discloses the 132 compounds T63.001 to T63.132    of the formula Ia, wherein R is CH₂CH₃, A is CH₂CHF₂, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 64: This table discloses the 132 compounds T64.001 to T64.132    of the formula Ia, wherein R is CH₂CH₃, A is CH₂CF₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 65: This table discloses the 132 compounds T65.001 to T65.132    of the formula Ia, wherein R is CH₂CH₃, A is benzyl, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 66: This table discloses the 132 compounds T66.001 to T66.132    of the formula Ia, wherein R is CH₂OCH₃, A is CH₃, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 67: This table discloses the 132 compounds T67.001 to T67.132    of the formula Ia, wherein R is CH₂OCH₃, A is CH₂CH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 68: This table discloses the 132 compounds T68.001 to T68.132    of the formula Ia, wherein R is CH₂OCH₃, A is i-C₃H₇, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 69: This table discloses the 132 compounds T69.001 to T69.132    of the formula Ia, wherein R is CH₂OCH₃, A is cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 70: This table discloses the 132 compounds T70.001 to T70.132    of the formula Ia, wherein R is CH₂OCH₃, A is CH₂-cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 71: This table discloses the 132 compounds T71.001 to T71.132    of the formula Ia, wherein R is CH₂OCH₃, A is CH₂OCH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 72: This table discloses the 132 compounds T72.001 to T72.132    of the formula Ia, wherein R is CH₂OCH₃, A is CH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 73: This table discloses the 132 compounds T73.001 to T73.132    of the formula Ia, wherein R is CH₂OCH₃, A is CH₂OCH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 74: This table discloses the 132 compounds T74.001 to T74.132    of the formula Ia, wherein R is CH₂OCH₃, A is CH₂CH₂OCH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 75: This table discloses the 132 compounds T75.001 to T75.132    of the formula Ia, wherein R is CH₂OCH₃, A is oxetan-3-yl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 76: This table discloses the 132 compounds T76.001 to T76.132    of the formula Ia, wherein R is CH₂OCH₃, A is CH₂CHF₂, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 77: This table discloses the 132 compounds T77.001 to T77.132    of the formula Ia, wherein R is CH₂OCH₃, A is CH₂CF₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 78: This table discloses the 132 compounds T78.001 to T78.132    of the formula Ia, wherein R is CH₂OCH₃, A is benzyl, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 79: This table discloses the 132 compounds T79.001 to T79.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is CH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 80: This table discloses the 132 compounds T80.001 to T80.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is CH₂CH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 81: This table discloses the 132 compounds T81.001 to T81.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is i-C₃H₇, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 82: This table discloses the 132 compounds T82.001 to T82.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 83: This table discloses the 132 compounds T83.001 to T83.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is CH₂-cyclopropyl, G    is chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 84: This table discloses the 132 compounds T84.001 to T84.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 85: This table discloses the 132 compounds T85.001 to T85.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is CH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 86: This table discloses the 132 compounds T86.001 to T86.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is CH₂OCH₂CH₂OCH₃, G    is chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 87: This table discloses the 132 compounds T87.001 to T87.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is CH₂CH₂OCH₂OCH₃, G    is chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 88: This table discloses the 132 compounds T88.001 to T88.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is oxetan-3-yl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 89: This table discloses the 132 compounds T89.001 to T89.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is CH₂CHF₂, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 90: This table discloses the 132 compounds T90.001 to T90.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is CH₂CF₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 91: This table discloses the 132 compounds T91.001 to T91.132    of the formula Ia, wherein R is CH₂CH₂OCH₃, A is benzyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 92: This table discloses the 132 compounds T92.001 to T92.132    of the formula Ia, wherein R is benzyl, A is CH₃, G is chlorine and    R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 93: This table discloses the 132 compounds T93.001 to T93.132    of the formula Ia, wherein R is benzyl, A is CH₂CH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 94: This table discloses the 132 compounds T94.001 to T94.132    of the formula Ia, wherein R is benzyl, A is i-C₃H₇, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 95: This table discloses the 132 compounds T95.001 to T95.132    of the formula Ia, wherein R is benzyl, A is cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 96: This table discloses the 132 compounds T96.001 to T96.132    of the formula Ia, wherein R is benzyl, A is CH₂-cyclopropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 97: This table discloses the 132 compounds T97.001 to T97.132    of the formula Ia, wherein R is benzyl, A is CH₂OCH₃, G is chlorine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 98: This table discloses the 132 compounds T98.001 to T98.132    of the formula Ia, wherein R is benzyl, A is CH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 99: This table discloses the 132 compounds T99.001 to T99.132    of the formula Ia, wherein R is benzyl, A is CH₂OCH₂CH₂OCH₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 100: This table discloses the 132 compounds T100.001 to    T100.132 of the formula Ia, wherein R is benzyl, A is    CH₂CH₂OCH₂OCH₃, G is chlorine and R_(a), R_(b), R_(c) and R_(d) are    as defined in Table 1.-   Table 101: This table discloses the 132 compounds T101.001 to    T101.132 of the formula Ia, wherein R is benzyl, A is oxetan-3-yl, G    is chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 102: This table discloses the 132 compounds T102.001 to    T102.132 of the formula Ia, wherein R is benzyl, A is CH₂CHF₂, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 103: This table discloses the 132 compounds T103.001 to    T103.132 of the formula Ia, wherein R is benzyl, A is CH₂CF₃, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.

Table 104: This table discloses the 132 compounds T104.001 to T104.132of the formula Ia, wherein R is benzyl, A is benzyl, G is chlorine andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

-   Table 105: This table discloses the 132 compounds T105.001 to    T105.132 of the formula Ia, wherein R is CH₃, A is methoxypropyl, G    is chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 106: This table discloses the 132 compounds T106.001 to    T106.132 of the formula Ia, wherein R is CH₃, A is    oxetan-3-ylmethyl, G is chlorine and R_(a), R_(b), R_(c) and R_(d)    are as defined in Table 1.-   Table 107: This table discloses the 132 compounds T107.001 to    T107.132 of the formula Ia, wherein R is CH₃, A is    tetrahydrofuran-2-ylmethyl, G is chlorine and R_(a), R_(b), R_(c)    and R_(d) are as defined in Table 1.-   Table 108: This table discloses the 132 compounds T108.001 to    T108.132 of the formula Ia, wherein R is CH₃, A is    tetrahydrofuran-3-ylmethyl, G is chlorine and R_(a), R_(b), R_(c)    and R_(d) are as defined in Table 1.-   Table 109: This table discloses the 132 compounds T109.001 to    T109.132 of the formula Ia, wherein R is CH₃, A is    tetrahydropyran-4-ylmethyl, G is chlorine and R_(a), R_(b), R_(c)    and R_(d) are as defined in Table 1.-   Table 110: This table discloses the 132 compounds T110.001 to    T110.132 of the formula Ia, wherein R is CH₃, A is methylthioethyl,    G is chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 111: This table discloses the 132 compounds T111.001 to    T111.132 of the formula Ia, wherein R is H, A is methoxypropyl, G is    chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 112: This table discloses the 132 compounds T112.001 to    T112.132 of the formula Ia, wherein R is CH₂CH₃, A is methoxypropyl,    G is chlorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 113: This table discloses the 132 compounds T113.001 to    T113.132 of the formula Ia, wherein R is CH₂CH₂OCH₃, A is    methoxypropyl, G is chlorine and R_(a), R_(b), R_(c) and R_(d) are    as defined in Table 1.-   Table 114: This table discloses the 132 compounds T114.001 to    T114.132 of the formula Ia, wherein R is H, A is    tetrahydrofuran-2-ylmethyl, G is chlorine and R_(a), R_(b), R_(c)    and R_(d) are as defined in Table 1.-   Table 115: This table discloses the 132 compounds T115.001 to    T115.132 of the formula Ia, wherein R is CH₂CH₃, A is    tetrahydrofuran-2-ylmethyl, G is chlorine and R_(a), R_(b), R_(c)    and R_(d) are as defined in Table 1.-   Table 116: This table discloses the 132 compounds T116.001 to    T116.132 of the formula Ia, wherein R is CH₂CH₂OCH₃, A is    tetrahydrofuran-2-ylmethyl, G is chlorine and R_(a), R_(b), R_(c)    and R_(d) are as defined in Table 1.-   Table 117: This table discloses the 132 compounds T117.001 to    T117.132 of the formula Ia, wherein R is CH₃, A is CH₃, G is bromine    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 118: This table discloses the 132 compounds T118.001 to    T118.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₃, G is    bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 119: This table discloses the 132 compounds T119.001 to    T119.132 of the formula Ia, wherein R is CH₃, A is i-C₃H₇, G is    bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 120: This table discloses the 132 compounds T120.001 to    T120.132 of the formula Ia, wherein R is CH₃, A is cyclopropyl, G is    bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 121: This table discloses the 132 compounds T121.001 to    T121.132 of the formula Ia, wherein R is CH₃, A is CH₂-cyclopropyl,    G is bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 122: This table discloses the 132 compounds T122.001 to    T122.132 of the formula Ia, wherein R is CH₃, A is CH₂OCH₃, G is    bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 123: This table discloses the 132 compounds T123.001 to    T123.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₂OCH₃, G is    bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 124: This table discloses the 132 compounds T124.001 to    T124.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₂CH₂OCH₃, G    is bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 125: This table discloses the 132 compounds T125.001 to    T125.132 of the formula Ia, wherein R is CH₃, A is CH₂OCH₂CH₂OCH₃, G    is bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 126: This table discloses the 132 compounds T126.001 to    T126.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₂OCH₂OCH₃, G    is bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 127: This table discloses the 132 compounds T127.001 to    T127.132 of the formula Ia, wherein R is CH₃, A is allyl, G is    bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 128: This table discloses the 132 compounds T128.001 to    T128.132 of the formula Ia, wherein R is CH₃, A is propargyl, G is    bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 129: This table discloses the 132 compounds T129.001 to    T129.132 of the formula Ia, wherein R is CH₃, A is benzyl, G is    bromine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 130: This table discloses the 132 compounds T130.001 to T130.132of the formula Ia, wherein R is CH₃, A is CH₃, G is fluorine and R_(a),R_(b), R_(c) and R_(d) are as defined in Table 1.

-   Table 131: This table discloses the 132 compounds T131.001 to    T131.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₃, G is    fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 132: This table discloses the 132 compounds T132.001 to    T132.132 of the formula Ia, wherein R is CH₃, A is i-C₃H₇, G is    fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 133: This table discloses the 132 compounds T133.001 to    T133.132 of the formula Ia, wherein R is CH₃, A is cyclopropyl, G is    fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 134: This table discloses the 132 compounds T134.001 to    T134.132 of the formula Ia, wherein R is CH₃, A is CH₂-cyclopropyl,    G is fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 135: This table discloses the 132 compounds T135.001 to    T135.132 of the formula Ia, wherein R is CH₃, A is CH₂OCH₃, G is    fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 136: This table discloses the 132 compounds T136.001 to    T136.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₂OCH₃, G is    fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 137: This table discloses the 132 compounds T137.001 to    T137.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₂CH₂OCH₃, G    is fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 138: This table discloses the 132 compounds T138.001 to    T138.132 of the formula Ia, wherein R is CH₃, A is CH₂OCH₂CH₂OCH₃, G    is fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 139: This table discloses the 132 compounds T139.001 to    T139.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₂OCH₂OCH₃, G    is fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in    Table 1.-   Table 140: This table discloses the 132 compounds T140.001 to    T140.132 of the formula Ia, wherein R is CH₃, A is allyl, G is    fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 141: This table discloses the 132 compounds T141.001 to    T141.132 of the formula Ia, wherein R is CH₃, A is propargyl, G is    fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 142: This table discloses the 132 compounds T142.001 to    T142.132 of the formula Ia, wherein R is CH₃, A is benzyl, G is    fluorine and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 143: This table discloses the 132 compounds T143.001 to    T143.132 of the formula Ia, wherein R is CH₃, A is CH₃, G is nitro    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 144: This table discloses the 132 compounds T144.001 to    T144.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₃, G is    nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 145: This table discloses the 132 compounds T145.001 to    T145.132 of the formula Ia, wherein R is CH₃, A is i-C₃H₇, G is    nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 146: This table discloses the 132 compounds T146.001 to T146.132of the formula Ia, wherein R is CH₃, A is cyclopropyl, G is nitro andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

-   Table 147: This table discloses the 132 compounds T147.001 to    T147.132 of the formula Ia, wherein R is CH₃, A is CH₂-cyclopropyl,    G is nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 148: This table discloses the 132 compounds T148.001 to    T148.132 of the formula Ia, wherein R is CH₃, A is CH₂OCH₃, G is    nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 149: This table discloses the 132 compounds T149.001 to    T149.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₂OCH₃, G is    nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 150: This table discloses the 132 compounds T150.001 to    T150.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₂CH₂OCH₃, G    is nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 151: This table discloses the 132 compounds T151.001 to    T151.132 of the formula Ia, wherein R is CH₃, A is CH₂OCH₂CH₂OCH₃, G    is nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 152: This table discloses the 132 compounds T152.001 to    T152.132 of the formula Ia, wherein R is CH₃, A is CH₂CH₂OCH₂OCH₃, G    is nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table    1.-   Table 153: This table discloses the 132 compounds T153.001 to    T153.132 of the formula Ia, wherein R is CH₃, A is allyl, G is nitro    and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 154: This table discloses the 132 compounds T154.001 to    T154.132 of the formula Ia, wherein R is CH₃, A is propargyl, G is    nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.-   Table 155: This table discloses the 132 compounds T155.001 to    T155.132 of the formula Ia, wherein R is CH₃, A is benzyl, G is    nitro and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

The compounds according to the invention are preventively and/orcuratively valuable active ingredients in the field of pest control,even at low rates of application, which have a very favorable biocidalspectrum and are well tolerated by warm-blooded species, fish andplants. The active ingredients according to the invention act againstall or individual developmental stages of normally sensitive, but alsoresistant, animal pests, such as insects or representatives of the orderAcarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly,i.e. in destruction of the pests, which takes place either immediatelyor only after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate, agood activity corresponding to a destruction rate (mortality) of atleast 50 to 60%. The compounds of formula I can be used to combat andcontrol infestations of insect pests such as Lepidoptera, Diptera,Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera,Siphonaptera, Hymenoptera and Isoptera and also other invertebratepests, for

example, acarine, nematode and mollusc pests. Insects, acarines,nematodes and molluscs are hereinafter collectively referred to aspests. The pests which may be combated and controlled by the use of theinvention compounds include those pests associated with agriculture(which term includes the growing of crops for food and fibre products),horticulture and animal husbandry, companion animals, forestry and thestorage of products of vegetable origin (such as fruit, grain andtimber); those pests associated with the damage of man-made structuresand the transmission of diseases of man and animals; and also nuisancepests (such as flies).

Examples of pest species which may be controlled by the compounds offormula I include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphisfabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids),Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper),Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp.(stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips),Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis(boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (whiteflies), Bemisia tabaci (white fly), Ostrinia nubilalis (European cornborer), Spodoptera littoralis (cotton leafworm), Heliothis virescens(tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpazea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pierisbrassicae (white butterfly), Plutella xylostella (diamond back moth),Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locustamigratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp.(rootworms), Panonychus ulmi (European red mite), Panonychus citri(citrus red mite), Tetranychus urticae (two-spotted spider mite),Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora(citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpusspp. (flat mites), Boophilus microplus (cattle tick), Dermacentorvariabilis (American dog tick), Ctenocephalides felis (cat flea),Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti(mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes),Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplanetaamericana (cockroach), Blatta orientalis (cockroach), termites of theMastotermitidae (for example Mastotermes spp.), the Kalotermitidae (forexample Neotermes spp.), the Rhinotermitidae (for example Coptotermesformosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R.hesperus, and R. santonensis) and the Termitidae (for exampleGlobitermes sulphureus), Solenopsis geminata (fire ant), Monomoriumpharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (bitingand sucking lice), Meloidogyne spp. (root knot nematodes), Globoderaspp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesionnematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulusspp. (citrus nematodes), Haemonchus contortus (barber pole worm),Caenorhabditis elegans (vinegar eelworm), Trichostrongylus spp. (gastrointestinal nematodes) and Deroceras reticulatum (slug).

Further examples of the above mentioned pests are:

-   from the order Acarina, for example,-   Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp.,    Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa,    Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,    Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp.,    Olygonychus pratensis, Ornithodoros spp., Panonychus spp.,    Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp.,    Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus    spp. and Tetranychus spp.;-   from the order Anoplura, for example,-   Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp.    and Phylloxera spp.;-   from the order Coleoptera, for example,-   Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema    tibialis, Cosmopolites spp., Curculio spp., Dermestes spp.,    Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa    decemLineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus    spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes    spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga    spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.;-   from the order Diptera, for example,-   Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora    erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp.,    Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp.,    Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp.,    Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp.,    Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami,    Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp.,    Tabanus spp., Tannia spp. and Tipula spp.;-   from the order Heteroptera, for example,-   Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp.,    Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp.,    Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and    Triatoma spp.;-   from the order Homoptera, for example,-   Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp.,    Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster    spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus    hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,    Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,    Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp.,    Parlatoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis    spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica,    Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,    Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes    vaporariorum, Trioza erytreae and Unaspis citri;-   from the order Hymenoptera, for example,-   Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae,    Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium    pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.;-   from the order Isoptera, for example,-   Reticulitermes spp.;-   from the order Lepidoptera, for example,-   Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama    argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,    Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella,    Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia    ambi-guella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,    Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta,    Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp.,    Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp.,    Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp.,    Hellula undalis, Hyphantria cunea, Keiferia lycopersicella,    Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria    spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca    sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis    spp., Panolis flammea, Pectinophora gossypiela, Phthorimaea    operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays    spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera    spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp.,    Trichoplusia ni and Yponomeuta spp.;-   from the order Mallophaga, for example,-   Damalinea spp. and Trichodectes spp.;-   from the order Orthoptera, for example,-   Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,    Locusta spp., Periplaneta spp. and Schistocerca spp.;-   from the order Psocoptera, for example,-   Liposcelis spp.;-   from the order Siphonaptera, for example,-   Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;-   from the order Thysanoptera, for example,-   Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii,    Taeniothrips spp., Thrips palmi and Thrips tabaci; and-   from the order Thysanura, for example,-   Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i.e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family, latex plants and ornamentals.

The term “crops” is to be understood as including also crops that havebeen rendered tolerant to herbicides like bromoxynil or classes ofherbicides (such as, for example, HPPD inhibitors, ALS inhibitors, forexample primisulfuron, prosulfuron and trifloxysulfuron, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors) as a result of conventional methodsof breeding or genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding (mutagenesis) is Clearfield® summer rape (Canola).Examples of crops that have been rendered tolerant to herbicides orclasses of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties commercially available underthe trade names RoundupReady® and LibertyLink®.

The term “crops” is also to be understood as including also crop plantswhich have been so transformed by the use of recombinant DNA techniquesthat they are capable of synthesising one or more selectively actingtoxins, such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b), CryIA(c),CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, orvegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsine inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2),CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidalproteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly alsohybrid toxins, truncated toxins and modified toxins. Hybrid toxins areproduced recombinantly by a new combination of different domains ofthose proteins (see, for example, WO 02/15701). Truncated toxins, forexample a truncated CryIA(b), are known. In the case of modified toxins,one or more amino acids of the naturally occurring toxin are replaced.In such amino acid replacements, preferably non-naturally presentprotease recognition sequences are inserted into the toxin, such as, forexample, in the case of CrylIIA055, a cathepsin-D-recognition sequenceis inserted into a CryIIIA toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cryl-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGardRootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGardPlus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin);Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I®(maize variety that expresses a CryIF(a2) toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a CryIA(c) toxin); Bollgard I® (cotton variety that expressesa CryIA(c) toxin); Bollgard II® (cotton variety that expresses aCryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expressesa VIP toxin); NewLeaf® (potato variety that expresses a CryIIIA toxin);Nature-Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

-   1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31    790 St. Sauveur, France, registration number C/FR/96/05/10.    Genetically modified Zea mays which has been rendered resistant to    attack by the European corn borer (Ostrinia nubilalis and Sesamia    nonagrioides) by transgenic expression of a truncated CryIA(b)    toxin. Bt11 maize also transgenically expresses the enzyme PAT to    achieve tolerance to the herbicide glufosinate ammonium.-   2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31    790 St. Sauveur, France, registration number C/FR/96/05/10.    Genetically modified Zea mays which has been rendered resistant to    attack by the European corn borer (Ostrinia nubilalis and Sesamia    nonagrioides) by transgenic expression of a CryIA(b) toxin. Bt176    maize also transgenically expresses the enzyme PAT to achieve    tolerance to the herbicide glufosinate ammonium.-   3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31    790 St. Sauveur, France, registration number C/FR/96/05/10. Maize    which has been rendered insect-resistant by transgenic expression of    a modified CryIIIA toxin. This toxin is Cry3A055 modified by    insertion of a cathepsin-D-protease recognition sequence. The    preparation of such transgenic maize plants is described in VVO    03/018810.-   4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de    Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.    MON 863 expresses a CryIIIB(b1) toxin and has resistance to certain    Coleoptera insects.-   5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de    Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.-   6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7    B-1160 Brussels, Belgium, registration number C/NL/00/10.    Genetically modified maize for the expression of the protein Cryl F    for achieving resistance to certain Lepidoptera insects and of the    PAT protein for achieving tolerance to the herbicide glufosinate    ammonium.-   7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de    Tervuren, B-1150 Brussels, Belgium, registration number    C/GB/02/M3/03. Consists of conventionally bred hybrid maize    varieties by crossing the genetically modified varieties NK603 and    MON 810. NK603×MON 810 Maize transgenically expresses the protein    CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts    tolerance to the herbicide Roundup® (contains glyphosate), and also    a CryIA(b) toxin obtained from Bacillus thuringiensis subsp.    kurstaki which brings about tolerance to certain Lepidoptera,    include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit and Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Base1, Switzerland) Report 2003.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, VVO 95/33818, and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Crops may also be modified for enhanced resistance to fungal (forexample Fusarium, Anthracnose, or Phytophthora), bacterial (for examplePseudomonas) or viral (for example potato leafroll virus, tomato spottedwilt virus, cucumber mosaic virus) pathogens.

Crops also include those that have enhanced resistance to nematodes,such as the soybean cyst nematode.

Crops that are tolerance to abiotic stress include those that haveenhanced tolerance to drought, high salt, high temperature, chill,frost, or light radiation, for example through expression of NF-YB orother proteins known in the art.

Crops that exhibit enhanced yield or quality include those with improvedflowering or fruit ripening properties (such as delayed ripening);modified oil, starch, amino acid, fatty acid, vitamin, phenolic or othercontent (such as Vistive™ soybean variety); enhanced nutrientutilisation (such as improved nitrogen assimilation); and enhancedquality plant product (such as higher quality cotton fibre).

Further areas of use of the compounds and compositions according to theinvention are the protection of stored goods and storerooms and theprotection of raw materials, such as wood, textiles, floor coverings orbuildings, and also in the hygiene sector, especially the protection ofhumans, domestic animals and productive livestock against pests of thementioned type.

In the hygiene sector, the compounds and compositions according to theinvention are active against ectoparasites such as hard ticks, softticks, mange mites, harvest mites, flies (biting and licking), parasiticfly larvae, lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorusspp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compounds and compositions according to the invention are alsosuitable for protecting against insect infestation in the case ofmaterials such as wood, textiles, plastics, adhesives, glues, paints,paper and card, leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharina.

The invention therefore provides a method of combating and controllinginsects, acarines, nematodes or molluscs which comprises applying aninsecticidally, acaricidally, nematicidally or molluscicidally effectiveamount of a compound of formula I, or a composition containing acompound of formula I, to a pest, a locus of pest, or to a plantsusceptible to attack by a pest, The compounds of formula I arepreferably used against insects or acarines.

The term “plant” as used herein includes seedlings, bushes and trees.

Besides displaying good insecticidal and acaricidal action andproperties, the active ingredient according to the invention arecharacterized by good plant/crop compatibility. Under different methodsof application, the compounds of the formula I, or compositions thereofaccording to the invention, demonstrate good plant/crop tolerancewhereby plant/crop damage (phytotoxicity) is significantly reduced. Theterms “crop” and “plant” are to be understood as defined above, whereasthe term “methods of application” is referred to below.

The invention therefore also relates to pesticidal compositions such asemulsifiable concentrates, suspension concentrates, directly sprayableor dilutable solutions, spreadable pastes, dilute emulsions, solublepowders, dispersible powders, wettable powders, dusts, granules orencapsulations in polymeric substances, which comprise—at least—one ofthe active ingredients according to the invention and which are to beselected to suit the intended aims and the prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, asolid active ingredient for example in a specific particle size, or,preferably, together with—at least—one of the auxiliaries conventionallyused in the art of formulation, such as extenders, for example solventsor solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partiallyhydrogenated aromatic hydrocarbons, preferably the fractions C8 to C12of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols such as ethanol, propanol or butanol,glycols and their ethers and esters such as propylene glycol,dipropylene glycol ether, ethylene glycol or ethylene glycol monomethylether or ethylene glycol monoethyl ether, ketones, such ascyclohexanone, isophorone or diacetone alcohol, strongly polar solvents,such as N-methylpyrrolid-2-one, dimethyl sulfoxide orN,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils,such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil,and silicone oils.

Solid carriers which are used for example for dusts and dispersiblepowders are, as a rule, ground natural minerals such as calcite, talc,kaolin, montmorillonite or attapulgite. To improve the physicalproperties, it is also possible to add highly disperse silicas or highlydisperse absorbtive polymers. Suitable particulate adsorptive carriersfor granules are porous types, such as pumice, brick grit, sepiolite orbentonite, and suitable non-sorptive carrier materials are calcite orsand. In addition, a large number of granulated materials of inorganicor organic nature can be used, in particular dolomite or comminutedplant residues.

Suitable surface-active compounds are, depending on the type of theactive ingredient to be formulated, non-ionic, cationic and/or anionicsurfactants or surfactant mixtures which have good emulsifying,dispersing and wetting properties. The surfactants mentioned below areonly to be considered as examples; a large number of further surfactantswhich are conventionally used in the art of formulation and suitableaccording to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, of saturated orunsaturated fatty acids or of alkyl phenols which may containapproximately 3 to approximately 30 glycol ether groups andapproximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatichydrocarbon radical or approximately 6 to approximately 18 carbon atomsin the alkyl moiety of the alkyl phenols. Also suitable arewater-soluble polyethylene oxide adducts with polypropylene glycol,ethylenediaminopo-dypropylene glycol or alkyl polypropylene glycolhaving 1 to approximately 10 carbon atoms in the alkyl chain andapproximately 20 to approximately 250 ethylene glycol ether groups andapproximately 10 to approximately 100 propylene glycol ether groups.Normally, the abovementioned compounds contain 1 to approximately 5ethylene glycol units per propylene glycol unit. Examples which may bementioned are nonylphenoxypolyethoxyethanol, castor oil polyglycolether, polypropylene glycol/polyethylene oxide adducts,tributylpheno-xypolyethoxyethanol, polyethylene glycol oroctylphenoxypolyethoxyethanol. Also suitable are fatty acid esters ofpolyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, especially, quarternary ammonium saltswhich generally have at least one alkyl radical of approximately 8 toapproximately 22 C atoms as substituents and as further substituents(unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzylradicals. The salts are preferably in the form of halides,methylsulfates or ethylsulfates. Examples are stearyltrimethylammoniumchloride and benzylbis(2-chloroethyl)ethyhammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps orwater-soluble synthetic surface-active compounds. Examples of suitablesoaps are the alkali, alkaline earth or (unsubstituted or substituted)ammonium salts of fatty acids having approximately 10 to approximately22 C atoms, such as the sodium or potassium salts of oleic or stearicacid, or of natural fatty acid mixtures which are obtainable for examplefrom coconut or tall oil; mention must also be made of the fatty acidmethyl taurates. However, synthetic surfactants are used morefrequently, in particular fatty sulfonates, fatty sulfates, sulfonatedbenzimidazole derivatives or alkylaryl sulfonates. As a rule, the fattysulfonates and fatty sulfates are present as alkali, alkaline earth or(substituted or unsubstituted) ammonium salts and they generally have analkyl radical of approximately 8 to approximately 22 C atoms, alkyl alsoto be understood as including the alkyl moiety of acyl radicals;examples which may be mentioned are the sodium or calcium salts oflignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcoholsulfate mixture prepared from natural fatty acids. This group alsoincludes the salts of the sulfuric esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonyl groups and a fatty acid radical ofapproximately 8 to approximately 22 C atoms. Examples ofalkylarylsulfonates are the sodium, calcium or triethanolammonium saltsof decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of anaphthalenesulfonic acid/formaldehyde condensate. Also possible are,furthermore, suitable phosphates, such as salts of the phosphoric esterof a p-nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.Further suitable phosphates are tris-esters of phosphoric acid withaliphatic or aromatic alcohols and/or bis-esters of alkyl phosphonicacids with aliphatic or aromatic alcohols, which are a high performanceoil-type adjuvant. These tris-esters have been described, for example,in WO0147356, WO0056146, EP-A-0579052 or EP-A-1018299 or arecommercially available under their chemical name. Preferred tris-estersof phosphoric acid for use in the new compositions aretris-(2-ethylhexyl) phosphate, tris-n-octyl phosphate andtris-butoxyethyl phosphate, where tris-(2-ethylhexyl) phosphate is mostpreferred. Suitable bis-ester of alkyl phosphonic acids arebis-(2-ethylhexyl)-(2-ethylhexyl)-phosphonate,bis-(2-ethylhexyl)-(n-octyl)-phosphonate, dibutyl-butyl phosphonate andbis(2-ethylhexyl)-tripropylene-phosphonate, wherebis-(2-ethylhexyl)-(n-octyl)-phosphonate is particularly preferred.

The compositions according to the invention can preferably additionallyinclude an additive comprising an oil of vegetable or animal origin, amineral oil, alkyl esters of such oils or mixtures of such oils and oilderivatives. The amount of oil additive used in the compositionaccording to the invention is generally from 0.01 to 10%, based on thespray mixture. For example, the oil additive can be added to the spraytank in the desired concentration after the spray mixture has beenprepared. Preferred oil additives comprise mineral oils or an oil ofvegetable origin, for example rapeseed oil such as ADIGOR® and MERO®,olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO®(Rhone-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin,for example the methyl derivatives, or an oil of animal origin, such asfish oil or beef tallow. A preferred additive contains, for example, asactive components essentially 80% by weight alkyl esters of fish oilsand 15% by weight methylated rapeseed oil, and also 5% by weight ofcustomary emulsifiers and pH modifiers. Especially preferred oiladditives comprise alkyl esters of C₈-C₂₂ fatty acids, especially themethyl derivatives of C₁₂-C₁₃ fatty acids, for example the methyl estersof lauric acid, palmitic acid and oleic acid, being important. Thoseesters are known as methyl laurate (CAS-111-82-0), methyl palmitate(CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acidmethyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those andother oil derivatives are also known from the Compendium of HerbicideAdjuvants, 5th Edition, Southern Illinois University, 2000. Also,alkoxylated fatty acids can be used as additives in the inventivecompositions as well as polymethylsiloxane based additives, which havebeen described in WO08/037373.

The application and action of the oil additives can be further improvedby combining them with surface-active substances, such as non-ionic,anionic or cationic surfactants.

Examples of suitable anionic, non-ionic and cationic surfactants arelisted on pages 7 and 8 of WO 97/34485. Preferred surface-activesubstances are anionic surfactants of the dodecylbenzylsulfonate type,especially the calcium salts thereof, and also non-ionic surfactants ofthe fatty alcohol ethoxylate type. Special preference is given toethoxylated C₁₂-C₂₂ fatty alcohols having a degree of ethoxylation offrom 5 to 40. Examples of commercially available surfactants are theGenapol types (Clariant AG). Also preferred are silicone surfactants,especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which arecommercially available e.g. as Silwet L-77®, and also perfluorinatedsurfactants. The concentration of surface-active substances in relationto the total additive is generally from 1 to 30% by weight. Examples ofoil additives that consist of mixtures of oils or mineral oils orderivatives thereof with surfactants are Edenor ME SU®, Turbocharge®(Syngenta AG, CH) and Actipron® (BP Oil UK Limited, GB).

The said surface-active substances may also be used in the formulationsalone, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oiladditive/surfactant mixture can contribute to a further enhancement ofaction. Suitable solvents are, for example, Solvesso® (ESSO) andAromatic Solvent® (Exxon Corporation). The concentration of suchsolvents can be from 10 to 80% by weight of the total weight. Such oiladditives, which may be in admixture with solvents, are described, forexample, in U.S. Pat. No. 4,834,908. A commercially available oiladditive disclosed therein is known by the name MERGE® (BASFCorporation). A further oil additive that is preferred according to theinvention is SCORE® (Syngenta Crop Protection Canada.)

In addition to the oil additives listed above, in order to enhance theactivity of the compositions according to the invention it is alsopossible for formulations of alkylpyrrolidones, (e.g. Agrimax®) to beadded to the spray mixture. Formulations of synthetic latices, such as,for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene(e.g. Bond®, Courier® or Emerald®) can also be used. Solutions thatcontain propionic acid, for example Eurogkem Pen-e-trate®, can also bemixed into the spray mixture as activity-enhancing agents.

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%,of active ingredient of thre formula land 1 to 99.9%, especially 5 to99.9%, of at least one solid or liquid adjuvant, it being possible as arule for 0 to 25%, especially 0.1 to 20%, of the composition to besurfactants(% in each case meaning percent by weight). Whereasconcentrated compositions tend to be preferred for commercial goods, theend consumer as a rule uses dilute compositions which have substantiallylower concentrations of active ingredient. Preferred compositions arecomposed in particular as follows (%=percent by weight):

Emulsifiable Concentrates:

-   active ingredient: 1 to 95%, preferably 5 to 50%, more preferably 5    to 20%-   surfactant: 1 to 30%, preferably 10 to 20%-   solvent: 5 to 98%, preferably 70 to 85%    Dusts:-   active ingredient: 0.1 to 10%, preferably 2 to 5%,-   solid carrier: 99.9 to 90%, preferably 99.9 to 99%    Suspension Concentrates:-   active ingredient: 5 to 75%, preferably 10 to 50%, more preferably    10 to 40%-   water: 94 to 24%, preferably 88 to 30%-   surfactant: 1 to 40%, preferably 2 to 30%    Oil-Based Suspension Concentrates:-   active ingredient: 2 to 75%, preferably 5 to 50%, more preferably 10    to 25%-   oil: 94 to 24%, preferably 88 to 30%-   surfactant: 1 to 40%, preferably 2 to 30%    Wettable Powders:-   active ingredient: 0.5 to 90%, preferably 1 to 80%, more preferably    25 to 75%-   surfactant: 0.5 to 20%, preferably 1 to 15%-   solid carrier: 5 to 99%, preferably 15 to 98%    Granulates:-   active ingredient: 0.5 to 30%, preferably 3 to 25%, more preferably    3 to 15%-   solid carrier: 99.5 to 70%, preferably 97 to 85%

Preferably, the term “active ingredient” refers to one of the compoundsselected from Tables 1 to 155 shown above. It also refers to mixtures ofthe compound of formula I, in particular a compound selected from saidTables 1 to 155, with other insecticides, fungicides, herbicides,safeners, adjuvants and the like, which mixtures are specificallydisclosed below.

The compositions can also comprise further solid or liquid auxiliaries,such as stabilizers, for example unepoxidized or epoxidized vegetableoils (for example epoxidized coconut oil, rapeseed oil or soya oil),antifoams, for example silicone oil, preservatives, viscosityregulators, binders and/or tackifiers; fertilizers, in particularnitrogen containing fertilizers such as ammonium nitrates and urea asdescribed in WO08/017388, which can enhance the efficacy of theinventive compounds; or other active ingredients for achieving specificeffects, for example ammonium or phosphonium salts, in particularhalides, (hydrogen)sulphates, nitrates, (hydrogen)carbonates, citrates,tartrates, formiates and acetates, as described in WO07/068427 andWO07/068428, which also can enhance the efficacy of the inventivecompounds and which can be used in combination with penetrationenhancers such as alkoxalated fatty acids; bactericides, fungicides,nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compositions according to the invention are also suitable for theprotection of plant propagation material, for example seeds, such asfruit, tubers or kernels, or nursery plants, against pests of theabovementioned type. The propagation material can be treated with thecompositions prior to planting, for example seed can be treated prior tosowing. Alternatively, the compositions can be applied to seed kernels(coating), either by soaking the kernels in a liquid composition or byapplying a layer of a solid composition. It is also possible to applythe compositions when the propagation material is planted to the site ofapplication, for example into the seed furrow during drilling. Thesetreatment methods for plant propagation material and the plantpropagation material thus treated are further subjects of the invention.

Further methods of application of the compositions according to theinvention comprise drip application onto the soil, dipping of parts ofplants such as roots bulbs or tubers, drenching the soil, as well assoil injection. These methods are known in the art.

In order to apply a compound of formula I as an insecticide, acaricide,nematicide or molluscicide to a pest, a locus of pest, or to a plantsusceptible to attack by a pest, a compound of formula I is usuallyformulated into a composition which includes, in addition to thecompound of formula I, a suitable inert diluent or carrier and,optionally, a formulation adjuvant in form of a surface active agent(SFA) as described herein or, for example, in EP-B-1062217. SFAs arechemicals which are able to modify the properties of an interface (forexample, liquid/solid, liquid/air or liquid/liquid interfaces) bylowering the interfacial tension and thereby leading to changes in otherproperties (for example dispersion, emulsification and wetting). It ispreferred that all compositions (both solid and liquid formulations)comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, forexample 5 to 60%, of a compound of formula I. The composition isgenerally used for the control of pests such that a compound of formulaI is applied at a rate of from 0.1 g to 10 kg per hectare, preferablyfrom 1 g to 6 kg per hectare, more preferably from 1 g to 1 kg perhectare.

When used in a seed dressing, a compound of formula I is used at a rateof 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably 0.005 gto 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.

In another aspect the present invention provides an insecticidal,acaricidal, nematicidal or molluscicidal composition comprising aninsecticidally, acaricidally, nematicidally or molluscicidally effectiveamount of a compound of formula I and a suitable carrier or diluenttherefor.

In a still further aspect the invention provides a method of combatingand controlling pests at a locus which comprises treating the pests orthe locus of the pests with an insecticidally, acaricidally,nematicidally or molluscicidally effective amount of a compositioncomprising a compound of formula I.

The compositions can be chosen from a number of formulation types,including dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (VVG), wettable powders (VVP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), micro-emulsions (ME), suspensionconcentrates (SC), oil-based suspension concentrate (OD), aerosols,fogging/smoke formulations, capsule suspensions (CS) and seed treatmentformulations. The formulation type chosen in any instance will dependupon the particular purpose en-visaged and the physical, chemical andbiological properties of the compound of formula I.

Dustable powders (DP) may be prepared by mixing a compound of formula Iwith one or more solid diluents (for example natural clays, kaolin,pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk,diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulphur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of formula Iwith one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulphate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (VVP) may be prepared by mixing a compound of formula Iwith one or more solid diluents or carriers, one or more wetting agentsand, preferably, one or more dispersing agents and, optionally, one ormore suspending agents to facilitate the dispersion in liquids. Themixture is then ground to a fine powder. Similar compositions may alsobe granulated to form water dispersible granules (VVG).

Granules (GR) may be formed either by granulating a mixture of acompound of formula I and one or more powdered solid diluents orcarriers, or from pre-formed blank granules by absorbing a compound offormula I (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller's earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of formula I (or a solution thereof, in a suitable agent) on toa hard core material (such as sands, silicates, mineral carbonates,sulphates or phosphates) and drying if necessary. Agents which arecommonly used to aid absorption or adsorption include solvents (such asaliphatic and aromatic petroleum solvents, alcohols, ethers, ketones andesters) and sticking agents (such as polyvinyl acetates, polyvinylalcohols, dextrins, sugars and vegetable oils). One or more otheradditives may also be included in granules (for example an emulsifyingagent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof formula I in water or an organic solvent, such as a ketone, alcoholor glycol ether. These solutions may contain a surface active agent (forexample to improve water dilution or prevent crystallisation in a spraytank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EVV) may beprepared by dissolving a compound of formula I in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone),dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide)and chlorinated hydrocarbons. An EC product may spontaneously emulsifyon addition to water, to produce an emulsion with sufficient stabilityto allow spray application through appropriate equipment. Preparation ofan EVV involves obtaining a compound of formula I either as a liquid (ifit is not a liquid at room temperature, it may be melted at a reasonabletemperature, typically below 70° C.) or in solution (by dissolving it inan appropriate solvent) and then emulsifiying the resultant liquid orsolution into water containing one or more SFAs, under high shear, toproduce an emulsion. Suitable solvents for use in EVVs include vegetableoils, chlorinated hydrocarbons (such as chlorobenzenes), aromaticsolvents (such as alkylbenzenes or alkylnaphthalenes) and otherappropriate organic solvents which have a low solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound offormula I is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in in ECs or in EWs. An ME may be either anoil-in-water or a water-in-oil system (which system is present may bedetermined by conductivity measurements) and may be suitable for mixingwater-soluble and oil-soluble pesticides in the same formulation. An MEis suitable for dilution into water, either remaining as a microemulsionor forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound offormula I. SCs may be prepared by ball or bead milling the solidcompound of formula I in a suitable medium, optionally with one or moredispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of formula I may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Oil-based suspension concentrate (OD) may be prepared similarly bysuspending finely divided insoluble solid particles of a compound offormula I in an organic fluid (for example at least one mineral oil orvegetable oil). ODs may further comprise at least one penetrationpromoter (for example an alcohol ethoxylate or a related compound), atleast one non-ionic surfactants and/or at least one anionic surfactant,and optionally at least one additive from the group of emulsifiers,foam-inhibiting agents, preservatives, anti-oxidants, dyestuffs, and/orinert filler materials. An OD is intended and suitable for dilution withwater before use to produce a spray solution with sufficient stabilityto allow spray application through appropriate equipment.

Aerosol formulations comprise a compound of formula I and a suitablepropellant (for example n-butane). A compound of formula I may also bedissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurised, hand-actuated spray pumps.

A compound of formula I may be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating, in an enclosedspace, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerisationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa compound of formula I and, optionally, a carrier or diluent therefor.The polymeric shell may be produced by either an interfacialpolycondensation reaction or by a coacervation procedure. Thecompositions may provide for controlled release of the compound offormula I and they may be used for seed treatment. A compound of formulaI may also be formulated in a biodegradable polymeric matrix to providea slow, controlled release of the compound.

A compound of formula I may also be formulated for use as a seedtreatment, for example as a powder composition, including a powder fordry seed treatment (DS), a water soluble powder (SS) or a waterdispersible powder for slurry treatment (WS), or as a liquidcomposition, including a flowable concentrate (FS), a solution (LS) or acapsule suspension (CS). The preparations of DS, SS, VVS, FS and LScompositions are very similar to those of, respectively, DP, SP, VVP,SC, OD and DC compositions described above. Compositions for treatingseed may include an agent for assisting the adhesion of the compositionto the seed (for example a mineral oil or a film-forming barrier).

A composition of the present invention may include one or more additivesto improve the biological performance of the composition (for example byimproving wetting, retention or distribution on surfaces; resistance torain on treated surfaces; or uptake or mobility of a compound of formulaI). Such additives include surface active agents (SFAs), spray additivesbased on oils, for example certain mineral oils, vegetable oils ornatural plant oils (such as soy bean and rape seed oil), and blends ofthese with other bio-enhancing adjuvants (ingredients which may aid ormodify the action of a compound of formula I). Increasing the effect ofa compound of formula I may for example be achieved by adding ammoniumand/or phosphonium salts, and/or optionally at least one penetrationpromotor such as fatty alcohol alkoxylates (for example rape oil methylester) or vegetable oil esters.

Wetting agents, dispersing agents and emulsifying agents may be surfaceactive agents (SFAs) of the cationic, anionic, amphoteric or non-ionictype.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulphuric acid (for example sodium laurylsulphate), salts of sulphonated aromatic compounds (for example sodiumdodecylbenzenesulphonate, calcium dodecylbenzenesulphonate,butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ethersulphates (for example sodium laureth-3-sulphate), ether carboxylates(for example sodium laureth-3-carboxylate), phosphate esters (productsfrom the reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulphosuccinamates, paraffin or olefine sulphonates, taurates andlignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonylphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

A compound of formula I may be applied by any of the known means ofapplying pesticidal compounds. For example, it may be applied,formulated or unformulated, to the pests or to a locus of the pests(such as a habitat of the pests, or a growing plant liable toinfestation by the pests) or to any part of the plant, including thefoliage, stems, branches or roots, to the seed before it is planted orto other media in which plants are growing or are to be planted (such assoil surrounding the roots, the soil generally, paddy water orhydroponic culture systems), directly or it may be sprayed on, dustedon, applied by dipping, applied as a cream or paste formulation, appliedas a vapour or applied through distribution or incorporation of acomposition (such as a granular composition or a composition packed in awater-soluble bag) in soil or an aqueous environment.

A compound of formula I may also be injected into plants or sprayed ontovegetation using electrodynamic spraying techniques or other low volumemethods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions ordispersions) are generally supplied in the form of a concentratecontaining a high proportion of the active ingredient, the concentratebeing added to water before use. These concentrates, which may includeDCs, SCs, ODs, ECs, EVVs, MEs SGs, SPs, VVPs, VVGs and CSs, are oftenrequired to withstand storage for prolonged periods and, after suchstorage, to be capable of addition to water to form aqueous preparationswhich remain homogeneous for a sufficient time to enable them to beapplied by conventional spray equipment. Such aqueous preparations maycontain varying amounts of a compound of formula I (for example 0.0001to 10%, by weight) depending upon the purpose for which they are to beused.

A compound of formula I may be used in mixtures with fertilisers (forexample nitrogen-, potassium- or phosphorus-containing fertilisers, andmore particularly ammonium nitrate and/or urea fertilizers). Suitableformulation types include granules of fertiliser. The mixtures suitablycontain up to 25% by weight of the compound of formula I.

The invention therefore also provides a fertiliser compositioncomprising a fertiliser and a compound of formula I.

The compositions of this invention may contain other compounds havingbiological activity, for example micronutrients or compounds havingfungicidal activity or which possess plant growth regulating,herbicidal, safening, insecticidal, nematicidal or acaricidal activity.

The compound of formula I may be the sole active ingredient of thecomposition or it may be admixed with one or more additional activeingredients such as a pesticide (insect, acarine, mollusc and nematodepesticide), fungicide, synergist, herbicide, safener or plant growthregulator where appropriate. The activity of the compositions accordingto the invention may thereby be broadened considerably and may havesurprising advantages which can also be described, in a wider sense, assynergistic activity. An additional active ingredient may: provide acomposition having a broader spectrum of activity or increasedpersistence at a locus; provide a composition demonstrating betterplant/crop tolerance by reducing phytotoxicity; provide a compositioncontrolling insects in their different development stages; synergise theactivity or complement the activity (for example by increasing the speedof effect or overcoming repellency) of the compound of formula I; orhelp to overcome or prevent the development of resistance to individualcomponents. The particular additional active ingredient will depend uponthe intended utility of the composition. Examples of suitable pesticidesinclude the following:

-   a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate,    esfenvalerate, deltamethrin, cyhalothrin (in particular    lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin,    tefluthrin, fish safe pyrethroids (for example ethofenprox), natural    pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or    5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropane    carboxylate;-   b) Organophosphates, such as, profenofos, sulprofos, acephate,    methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos,    thiometon, fenamiphos, monocrotophos, profenofos, triazophos,    methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos,    phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim,    pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or    diazinon;-   c) Carbamates (including aryl carbamates), such as pirimicarb,    triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb,    aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur,    methomyl or oxamyl;-   d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron,    flufenoxuron or chlorfluazuron;-   e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or    azocyclotin;-   f) Pyrazoles, such as tebufenpyrad and fenpyroximate;-   g) Macrolides, such as avermectins or milbemycins, for example    abamectin, emamectin benzoate, ivermectin, milbemycin, or spinosad,    spinetoram or azadirachtin;-   h) Hormones or pheromones;-   i) Organochlorine compounds such as endosulfan, benzene    hexachloride, DDT, chlordane or dieldrin;-   j) Amidines, such as chlordimeform or amitraz;-   k) Fumigant agents, such as chloropicrin, dichloropropane, methyl    bromide or metam;-   l) Neonicotinoid compounds such as imidacloprid, thiacloprid,    acetamiprid, clothianidin, nitenpyram, dinotefuran or thiamethoxam;-   m) Diacylhydrazines, such as tebufenozide, chromafenozide or    methoxyfenozide;-   n) Diphenyl ethers, such as diofenolan or pyriproxifen;-   j) lndoxacarb;-   p) Chlorfenapyr;-   q) Pymetrozine or pyrifluquinazon;-   r) Spirotetramat, spirodiclofen or spiromesifen;-   s) Flubendiamide, chloranthraliniprole, or cyanthraniliprole;-   t) Cyenopyrafen or cyflumetofen; or-   u) Sulfoxaflor.

In addition to the major chemical classes of pesticide listed above,other pesticides having particular targets may be employed in thecomposition, if appropriate for the intended utility of the composition.For instance, selective insecticides for particular crops, for examplestemborer specific insecticides (such as cartap) or hopper specificinsecticides (such as buprofezin) for use in rice may be employed.Alternatively insecticides or acaricides specific for particular insectspecies/stages may also be included in the compositions (for exampleacaricidal ovo-larvicides, such as clofentezine, flubenzimine,hexythiazox or tetradifon; acaricidal motilicides, such as dicofol orpropargite; acaricides, such as bromopropylate or chlorobenzilate; orgrowth regulators, such as hydramethylnon, cyromazine, methoprene,chlorfluazuron or diflubenzuron).

The following mixtures of the compounds of formula I with activeingredients are preferred, wherein, preferably, the term “COMPOUND OFFORMULA I” refers to a compound selected from the Tables 1 to 155:

-   -   an adjuvant selected from the group of substances consisting of        an oil of vegetable or animal origin, a mineral oil, alkyl        esters of such oils or mixtures of such oils, and petroleum oils        (alternative name) (628)+COMPOUND OF FORMULA I,    -   an acaricide selected from the group of substances consisting of        1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name)        (910)+COMPOUND OF FORMULA I, 2,4-dichlorophenyl benzenesulfonate        (IUPAC/Chemical Abstracts name) (1059)+COMPOUND OF FORMULA I,        2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name)        (1295)+COMPOUND OF FORMULA I, 4-chlorophenyl phenyl sulfone        (IUPAC name) (981)+COMPOUND OF FORMULA I, abamectin (1)+COMPOUND        OF FORMULA I, acequinocyl (3)+COMPOUND OF FORMULA I, acetoprole        [CCN]+COMPOUND OF FORMULA I, acrinathrin (9)+COMPOUND OF FORMULA        I, aldicarb (16)+COMPOUND OF FORMULA I, aldoxycarb        (863)+COMPOUND OF FORMULA I, alpha-cypermethrin (202)+COMPOUND        OF FORMULA I, amidithion (870)+COMPOUND OF FORMULA I,        amidoflumet [CCN]+COMPOUND OF FORMULA I, amidothioate        (872)+COMPOUND OF FORMULA I, amiton (875)+COMPOUND OF FORMULA I,        amiton hydrogen oxalate (875)+COMPOUND OF FORMULA I, amitraz        (24)+COMPOUND OF FORMULA I, aramite (881)+COMPOUND OF FORMULA I,        arsenous oxide (882)+COMPOUND OF FORMULA I, AVI 382 (compound        code)+COMPOUND OF FORMULA I, AZ 60541 (compound code)+COMPOUND        OF FORMULA I, azinphos-ethyl (44)+COMPOUND OF FORMULA I,        azinphos-methyl (45)+COMPOUND OF FORMULA I, azobenzene (IUPAC        name) (888)+COMPOUND OF FORMULA I, azocyclotin (46)+COMPOUND OF        FORMULA I, azothoate (889)+COMPOUND OF FORMULA I, benomyl        (62)+COMPOUND OF FORMULA I, benoxafos (alternative name)        [CCN]+COMPOUND OF FORMULA I, benzoximate (71)+COMPOUND OF        FORMULA I, benzyl benzoate (IUPAC name) [CCN]+COMPOUND OF        FORMULA I, bifenazate (74)+COMPOUND OF FORMULA I, bifenthrin        (76)+COMPOUND OF FORMULA I, binapacryl (907)+COMPOUND OF FORMULA        I, brofenvalerate (alternative name)+COMPOUND OF FORMULA I,        bromocyclen (918)+COMPOUND OF FORMULA I, bromophos        (920)+COMPOUND OF FORMULA I, bromophos-ethyl (921)+COMPOUND OF        FORMULA I, bromopropylate (94)+COMPOUND OF FORMULA I, buprofezin        (99)+COMPOUND OF FORMULA I, butocarboxim (103)+COMPOUND OF        FORMULA I, butoxycarboxim (104)+COMPOUND OF FORMULA I,        butylpyridaben (alternative name)+COMPOUND OF FORMULA I, calcium        polysulfide (IUPAC name) (111)+COMPOUND OF FORMULA I,        camphechlor (941)+COMPOUND OF FORMULA I, carbanolate        (943)+COMPOUND OF FORMULA I, carbaryl (115)+COMPOUND OF FORMULA        I, carbofuran (118)+COMPOUND OF FORMULA I, carbophenothion        (947)+COMPOUND OF FORMULA I, CGA 50′439 (development code)        (125)+COMPOUND OF FORMULA I, chinomethionat (126)+COMPOUND OF        FORMULA I, chlorbenside (959)+COMPOUND OF FORMULA I,        chlordimeform (964)+COMPOUND OF FORMULA I, chlordimeform        hydrochloride (964)+COMPOUND OF FORMULA I, chlorfenapyr        (130)+COMPOUND OF FORMULA I, chlorfenethol (968)+COMPOUND OF        FORMULA I, chlorfenson (970)+COMPOUND OF FORMULA I,        chlorfensulphide (971)+COMPOUND OF FORMULA I, chlorfenvinphos        (131)+COMPOUND OF FORMULA I, chlorobenzilate (975)+COMPOUND OF        FORMULA I, chloromebuform (977)+COMPOUND OF FORMULA I,        chloromethiuron (978)+COMPOUND OF FORMULA I, chloropropylate        (983)+COMPOUND OF FORMULA I, chlorpyrifos (145)+COMPOUND OF        FORMULA I, chlorpyrifos-methyl (146)+COMPOUND OF FORMULA I,        chlorthiophos (994)+COMPOUND OF FORMULA I, cinerin I        (696)+COMPOUND OF FORMULA I, cinerin II (696)+COMPOUND OF        FORMULA I, cinerins (696)+COMPOUND OF FORMULA I, clofentezine        (158)+COMPOUND OF FORMULA I, closantel (alternative name)        [CCN]+COMPOUND OF FORMULA I, coumaphos (174)+COMPOUND OF FORMULA        I, crotamiton (alternative name) [CCN]+COMPOUND OF FORMULA I,        crotoxyphos (1010)+COMPOUND OF FORMULA I, cufraneb        (1013)+COMPOUND OF FORMULA I, cyanthoate (1020)+COMPOUND OF        FORMULA I, cyenopyrafen [CCN]+COMPOUND OF FORMULA I,        cyflumetofen (CAS Reg. No.: 400882-07-7)+COMPOUND OF FORMULA I,        cyhalothrin (196)+COMPOUND OF FORMULA I, cyhexatin        (199)+COMPOUND OF FORMULA I, cypermethrin (201)+COMPOUND OF        FORMULA I, DCPM (1032)+COMPOUND OF FORMULA I, DDT (219)+COMPOUND        OF FORMULA I, demephion (1037)+COMPOUND OF FORMULA I,        demephion-O (1037)+COMPOUND OF FORMULA I, demephion-S        (1037)+COMPOUND OF FORMULA I, demeton (1038)+COMPOUND OF FORMULA        I, demeton-methyl (224)+COMPOUND OF FORMULA I, demeton-O        (1038)+COMPOUND OF FORMULA I, demeton-O-methyl (224)+COMPOUND OF        FORMULA I, demeton-S (1038)+COMPOUND OF FORMULA I,        demeton-5-methyl (224)+COMPOUND OF FORMULA I,        demeton-5-methylsulphon (1039)+COMPOUND OF FORMULA I,        diafenthiuron (226)+COMPOUND OF FORMULA I, dialifos        (1042)+COMPOUND OF FORMULA I, diazinon (227)+COMPOUND OF FORMULA        I, dichlofluanid (230)+COMPOUND OF FORMULA I, dichlorvos        (236)+COMPOUND OF FORMULA I, dicliphos (alternative        name)+COMPOUND OF FORMULA I, dicofol (242)+COMPOUND OF FORMULA        I, dicrotophos (243)+COMPOUND OF FORMULA I, dienochlor        (1071)+COMPOUND OF FORMULA I, diflovidazin [CCN]+COMPOUND OF        FORMULA I, dimefox (1081)+COMPOUND OF FORMULA I, dimethoate        (262)+COMPOUND OF FORMULA I, dinactin (alternative name)        (653)+COMPOUND OF FORMULA I, dinex (1089)+COMPOUND OF FORMULA I,        dinex-diclexine (1089)+COMPOUND OF FORMULA I, dinobuton        (269)+COMPOUND OF FORMULA I, dinocap (270)+COMPOUND OF FORMULA        I, dinocap-4 [CCN]+COMPOUND OF FORMULA I, dinocap-6        [CCN]+COMPOUND OF FORMULA I, dinocton (1090)+COMPOUND OF FORMULA        I, dino-penton (1092)+COMPOUND OF FORMULA I, dinosulfon        (1097)+COMPOUND OF FORMULA I, dinoterbon (1098)+COMPOUND OF        FORMULA I, dioxathion (1102)+COMPOUND OF FORMULA I, diphenyl        sulfone (IUPAC name) (1103)+COMPOUND OF FORMULA I, disulfuram        (alternative name) [CCN]+COMPOUND OF FORMULA I, disulfoton        (278)+COMPOUND OF FORMULA I, DNOC (282)+COMPOUND OF FORMULA I,        dofenapyn (1113)+COMPOUND OF FORMULA I, doramectin (alternative        name) [CCN]+COMPOUND OF FORMULA I, endosulfan (294)+COMPOUND OF        FORMULA I, endothion (1121)+COMPOUND OF FORMULA I, EPN        (297)+COMPOUND OF FORMULA I, eprinomectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, ethion (309)+COMPOUND OF FORMULA I,        ethoate-methyl (1134)+COMPOUND OF FORMULA I, etoxazole        (320)+COMPOUND OF FORMULA I, etrimfos (1142)+COMPOUND OF FORMULA        I, fenazaflor (1147)+COMPOUND OF FORMULA I, fenazaquin        (328)+COMPOUND OF FORMULA I, fenbutatin oxide (330)+COMPOUND OF        FORMULA I, fenothiocarb (337)+COMPOUND OF FORMULA I,        fenpropathrin (342)+COMPOUND OF FORMULA I, fenpyrad (alternative        name)+COMPOUND OF FORMULA I, fenpyroximate (345)+COMPOUND OF        FORMULA I, fenson (1157)+COMPOUND OF FORMULA I, fentrifanil        (1161)+COMPOUND OF FORMULA I, fenvalerate (349)+COMPOUND OF        FORMULA I, fipronil (354)+COMPOUND OF FORMULA I, fluacrypyrim        (360)+COMPOUND OF FORMULA I, fluazuron (1166)+COMPOUND OF        FORMULA I, flubenzimine (1167)+COMPOUND OF FORMULA I,        flucycloxuron (366)+COMPOUND OF FORMULA I, flucythrinate        (367)+COMPOUND OF FORMULA I, fluenetil (1169)+COMPOUND OF        FORMULA I, flufenoxuron (370)+COMPOUND OF FORMULA I, flumethrin        (372)+COMPOUND OF FORMULA I, fluorbenside (1174)+COMPOUND OF        FORMULA I, fluvalinate (1184)+COMPOUND OF FORMULA I, FMC 1137        (development code) (1185)+COMPOUND OF FORMULA I, formetanate        (405)+COMPOUND OF FORMULA I, formetanate hydrochloride        (405)+COMPOUND OF FORMULA I, formothion (1192)+COMPOUND OF        FORMULA I, formparanate (1193)+COMPOUND OF FORMULA I, gamma-HCH        (430)+COMPOUND OF FORMULA I, glyodin (1205)+COMPOUND OF FORMULA        I, halfenprox (424)+COMPOUND OF FORMULA I, heptenophos        (432)+COMPOUND OF FORMULA I, hexadecyl cyclopropanecarboxylate        (IUPAC/Chemical Abstracts name) (1216)+COMPOUND OF FORMULA I,        hexythiazox (441)+COMPOUND OF FORMULA I, IKA 2002 (CAS Reg. No.:        211923-74-9)+COMPOUND OF FORMULA I, iodomethane (IUPAC name)        (542)+COMPOUND OF FORMULA I, isocarbophos (alternative name)        (473)+COMPOUND OF FORMULA I, isopropyl        O-(methoxyaminothiophosphoryl)salicylate (IUPAC name)        (473)+COMPOUND OF FORMULA I, ivermectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, jasmolin I (696)+COMPOUND OF        FORMULA I, jasmolin II (696)+COMPOUND OF FORMULA I, jodfenphos        (1248)+COMPOUND OF FORMULA I, lindane (430)+COMPOUND OF FORMULA        I, lufenuron (490)+COMPOUND OF FORMULA I, malathion        (492)+COMPOUND OF FORMULA I, malonoben (1254)+COMPOUND OF        FORMULA I, mecarbam (502)+COMPOUND OF FORMULA I, mephosfolan        (1261)+COMPOUND OF FORMULA I, mesulfen (alternative name)        [CCN]+COMPOUND OF FORMULA I, methacrifos (1266)+COMPOUND OF        FORMULA I, methamidophos (527)+COMPOUND OF FORMULA I,        methidathion (529)+COMPOUND OF FORMULA I, methiocarb        (530)+COMPOUND OF FORMULA I, methomyl (531)+COMPOUND OF FORMULA        I, methyl bromide (537)+COMPOUND OF FORMULA I, metolcarb        (550)+COMPOUND OF FORMULA I, mevinphos (556)+COMPOUND OF FORMULA        I, mexacarbate (1290)+COMPOUND OF FORMULA I, milbemectin        (557)+COMPOUND OF FORMULA I, milbemycin oxime (alternative name)        [CCN]+COMPOUND OF FORMULA I, mipafox (1293)+COMPOUND OF FORMULA        I, monocrotophos (561)+COMPOUND OF FORMULA I, morphothion        (1300)+COMPOUND OF FORMULA I, moxidectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, naled (567)+COMPOUND OF FORMULA I,        NC-184 (compound code)+COMPOUND OF FORMULA I, NC-512 (compound        code)+COMPOUND OF FORMULA I, nifluridide (1309)+COMPOUND OF        FORMULA I, nikkomycins (alternative name) [CCN]+COMPOUND OF        FORMULA I, nitrilacarb (1313)+COMPOUND OF FORMULA I, nitrilacarb        1:1 zinc chloride complex (1313)+COMPOUND OF FORMULA I, NNI-0101        (compound code)+COMPOUND OF FORMULA I, NNI-0250 (compound        code)+COMPOUND OF FORMULA I, omethoate (594)+COMPOUND OF FORMULA        I, oxamyl (602)+COMPOUND OF FORMULA I, oxydeprofos        (1324)+COMPOUND OF FORMULA I, oxydisulfoton (1325)+COMPOUND OF        FORMULA I, pp′-DDT (219)+COMPOUND OF FORMULA I, parathion        (615)+COMPOUND OF FORMULA I, permethrin (626)+COMPOUND OF        FORMULA I, petroleum oils (alternative name) (628)+COMPOUND OF        FORMULA I, phenkapton (1330)+COMPOUND OF FORMULA I, phenthoate        (631)+COMPOUND OF FORMULA I, phorate (636)+COMPOUND OF FORMULA        I, phosalone (637)+COMPOUND OF FORMULA I, phosfolan        (1338)+COMPOUND OF FORMULA I, phosmet (638)+COMPOUND OF FORMULA        I, phosphamidon (639)+COMPOUND OF FORMULA I, phoxim        (642)+COMPOUND OF FORMULA I, pirimiphos-methyl (652)+COMPOUND OF        FORMULA I, polychloroterpenes (traditional name) (1347)+COMPOUND        OF FORMULA I, polynactins (alternative name) (653)+COMPOUND OF        FORMULA I, proclonol (1350)+COMPOUND OF FORMULA I, profenofos        (662)+COMPOUND OF FORMULA I, promacyl (1354)+COMPOUND OF FORMULA        I, propargite (671)+COMPOUND OF FORMULA I, propetamphos        (673)+COMPOUND OF FORMULA I, propoxur (678)+COMPOUND OF FORMULA        I, prothidathion (1360)+COMPOUND OF FORMULA I, prothoate        (1362)+COMPOUND OF FORMULA I, pyrethrin I (696)+COMPOUND OF        FORMULA I, pyrethrin II (696)+COMPOUND OF FORMULA I, pyrethrins        (696)+COMPOUND OF FORMULA I, pyridaben (699)+COMPOUND OF FORMULA        I, pyridaphenthion (701)+COMPOUND OF FORMULA I, pyrimidifen        (706)+COMPOUND OF FORMULA I, pyrimitate (1370)+COMPOUND OF        FORMULA I, quinalphos (711)+COMPOUND OF FORMULA I, quintiofos        (1381)+COMPOUND OF FORMULA I, R-1492 (development code)        (1382)+COMPOUND OF FORMULA I, RA-17 (development code)        (1383)+COMPOUND OF FORMULA I, rotenone (722)+COMPOUND OF FORMULA        I, schradan (1389)+COMPOUND OF FORMULA I, sebufos (alternative        name)+COMPOUND OF FORMULA I, selamectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, SI-0009 (compound code)+COMPOUND OF        FORMULA I, sophamide (1402)+COMPOUND OF FORMULA I, spirodiclofen        (738)+COMPOUND OF FORMULA I, spiromesifen (739)+COMPOUND OF        FORMULA I, SSI-121 (development code) (1404)+COMPOUND OF FORMULA        I, sulfuram (alternative name) [CCN]+COMPOUND OF FORMULA I,        sulfluramid (750)+COMPOUND OF FORMULA I, sulfotep (753)+COMPOUND        OF FORMULA I, sulfur (754)+COMPOUND OF FORMULA I, SZI-121        (development code) (757)+COMPOUND OF FORMULA I, tau-fluvalinate        (398)+COMPOUND OF FORMULA I, tebufenpyrad (763)+COMPOUND OF        FORMULA I, TEPP (1417)+COMPOUND OF FORMULA I, terbam        (alternative name)+COMPOUND OF FORMULA I, tetrachlorvinphos        (777)+COMPOUND OF FORMULA I, tetradifon (786)+COMPOUND OF        FORMULA I, tetranactin (alternative name) (653)+COMPOUND OF        FORMULA I, tetrasul (1425)+COMPOUND OF FORMULA I, thiafenox        (alternative name)+COMPOUND OF FORMULA I, thiocarboxime        (1431)+COMPOUND OF FORMULA I, thiofanox (800)+COMPOUND OF        FORMULA I, thiometon (801)+COMPOUND OF FORMULA I, thioquinox        (1436)+COMPOUND OF FORMULA I, thuringiensin (alternative name)        [CCN]+COMPOUND OF FORMULA I, triamiphos (1441)+COMPOUND OF        FORMULA I, triarathene (1443)+COMPOUND OF FORMULA I, triazophos        (820)+COMPOUND OF FORMULA I, triazuron (alternative        name)+COMPOUND OF FORMULA I, trichlorfon (824)+COMPOUND OF        FORMULA I, trifenofos (1455)+COMPOUND OF FORMULA I, trinactin        (alternative name) (653)+COMPOUND OF FORMULA I, vamidothion        (847)+COMPOUND OF FORMULA I, vaniliprole [CCN] and YI-5302        (compound code)+COMPOUND OF FORMULA I,    -   an algicide selected from the group of substances consisting of        bethoxazin [CCN]+COMPOUND OF FORMULA I, copper dioctanoate        (IUPAC name) (170)+COMPOUND OF FORMULA I, copper sulfate        (172)+COMPOUND OF FORMULA I, cybutryne [CCN]+COMPOUND OF FORMULA        I, dichlone (1052)+COMPOUND OF FORMULA I, dichlorophen        (232)+COMPOUND OF FORMULA I, endothal (295)+COMPOUND OF FORMULA        I, fentin (347)+COMPOUND OF FORMULA I, hydrated lime        [CCN]+COMPOUND OF FORMULA I, nabam (566)+COMPOUND OF FORMULA I,        quinoclamine (714)+COMPOUND OF FORMULA I, quinonamid        (1379)+COMPOUND OF FORMULA I, simazine (730)+COMPOUND OF FORMULA        I, triphenyltin acetate (IUPAC name) (347) and triphenyltin        hydroxide (IUPAC name) (347)+COMPOUND OF FORMULA I,    -   an anthelmintic selected from the group of substances consisting        of abamectin (1)+COMPOUND OF FORMULA I, crufomate        (1011)+COMPOUND OF FORMULA I, doramectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, emamectin (291)+COMPOUND OF FORMULA        I, emamectin benzoate (291)+COMPOUND OF FORMULA I, eprinomectin        (alternative name) [CCN]+COMPOUND OF FORMULA I, ivermectin        (alternative name) [CCN]+COMPOUND OF FORMULA I, milbemycin oxime        (alternative name) [CCN]+COMPOUND OF FORMULA I, moxidectin        (alternative name) [CCN]+COMPOUND OF FORMULA I, piperazine        [CCN]+COMPOUND OF FORMULA I, selamectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, spinosad (737) and thiophanate        (1435)+COMPOUND OF FORMULA I,    -   an avicide selected from the group of substances consisting of        chloralose (127)+COMPOUND OF FORMULA I, endrin (1122)+COMPOUND        OF FORMULA I, fenthion (346)+COMPOUND OF FORMULA I,        pyridin-4-amine (IUPAC name) (23) and strychnine (745)+COMPOUND        OF FORMULA I,    -   a bactericide selected from the group of substances consisting        of 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+COMPOUND        OF FORMULA 1,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC        name) (748)+COMPOUND OF FORMULA 1,8-hydroxyquinoline sulfate        (446)+COMPOUND OF FORMULA I, bronopol (97)+COMPOUND OF FORMULA        I, copper dioctanoate (IUPAC name) (170)+COMPOUND OF FORMULA I,        copper hydroxide (IUPAC name) (169)+COMPOUND OF FORMULA I,        cresol [CCN]+COMPOUND OF FORMULA I, dichlorophen (232)+COMPOUND        OF FORMULA I, dipyrithione (1105)+COMPOUND OF FORMULA I, dodicin        (1112)+COMPOUND OF FORMULA I, fenaminosulf (1144)+COMPOUND OF        FORMULA I, formaldehyde (404)+COMPOUND OF FORMULA I,        hydrargaphen (alternative name) [CCN]+COMPOUND OF FORMULA I,        kasugamycin (483)+COMPOUND OF FORMULA I, kasugamycin        hydrochloride hydrate (483)+COMPOUND OF FORMULA I, nickel        bis(dimethyldithiocarbamate) (IUPAC name) (1308)+COMPOUND OF        FORMULA I, nitrapyrin (580)+COMPOUND OF FORMULA I, octhilinone        (590)+COMPOUND OF FORMULA I, oxolinic acid (606)+COMPOUND OF        FORMULA I, oxytetracycline (611)+COMPOUND OF FORMULA I,        potassium hydroxyquinoline sulfate (446)+COMPOUND OF FORMULA I,        probenazole (658)+COMPOUND OF FORMULA I, streptomycin        (744)+COMPOUND OF FORMULA I, streptomycin sesquisulfate        (744)+COMPOUND OF FORMULA I, tecloftalam (766)+COMPOUND OF        FORMULA I, and thiomersal (alternative name) [CCN]+COMPOUND OF        FORMULA I,    -   a biological agent selected from the group of substances        consisting of Adoxophyes orana GV (alternative name)        (12)+COMPOUND OF FORMULA I, Agrobacterium radiobacter        (alternative name) (13)+COMPOUND OF FORMULA I, Amblyseius spp.        (alternative name) (19)+COMPOUND OF FORMULA I, Anagrapha        falcifera NPV (alternative name) (28)+COMPOUND OF FORMULA I,        Anagrus atomus (alternative name) (29)+COMPOUND OF FORMULA I,        Aphelinus abdominalis (alternative name) (33)+COMPOUND OF        FORMULA I, Aphidius colemani (alternative name) (34)+COMPOUND OF        FORMULA I, Aphidoletes aphidimyza (alternative name)        (35)+COMPOUND OF FORMULA I, Autographa californica NPV        (alternative name) (38)+COMPOUND OF FORMULA I, Bacillus firmus        (alternative name) (48)+COMPOUND OF FORMULA I, Bacillus        sphaericus Neide (scientific name) (49)+COMPOUND OF FORMULA I,        Bacillus thuringiensis Berliner (scientific name) (51)+COMPOUND        OF FORMULA I, Bacillus thuringiensis subsp. aizawai (scientific        name) (51)+COMPOUND OF FORMULA I, Bacillus thuringiensis subsp.        israelensis (scientific name) (51)+COMPOUND OF FORMULA I,        Bacillus thuringiensis subsp. japonensis (scientific name)        (51)+COMPOUND OF FORMULA I, Bacillus thuringiensis subsp.        kurstaki (scientific name) (51)+COMPOUND OF FORMULA I, Bacillus        thuringiensis subsp. tenebrionis (scientific name) (51)+COMPOUND        OF FORMULA I, Beauveria bassiana (alternative name)        (53)+COMPOUND OF FORMULA I, Beauveria brongniartii (alternative        name) (54)+COMPOUND OF FORMULA I, Chrysoperla carnea        (alternative name) (151)+COMPOUND OF FORMULA I, Cryptolaemus        montrouzieri (alternative name) (178)+COMPOUND OF FORMULA I,        Cydia pomonella GV (alternative name) (191)+COMPOUND OF FORMULA        I, Dacnusa sibirica (alternative name) (212)+COMPOUND OF FORMULA        I, Diglyphus isaea (alternative name) (254)+COMPOUND OF FORMULA        I, Encarsia formosa (scientific name) (293)+COMPOUND OF FORMULA        I, Eretmocerus eremicus (alternative name) (300)+COMPOUND OF        FORMULA I, Helicoverpa zea NPV (alternative name) (431)+COMPOUND        OF FORMULA I, Heterorhabditis bacteriophora and H. megidis        (alternative name) (433)+COMPOUND OF FORMULA I, Hippodamia        convergens (alternative name) (442)+COMPOUND OF FORMULA I,        Leptomastix dactylopii (alternative name) (488)+COMPOUND OF        FORMULA I, Macrolophus caliginosus (alternative name)        (491)+COMPOUND OF FORMULA I, Mamestra brassicae NPV (alternative        name) (494)+COMPOUND OF FORMULA I, Metaphycus helvolus        (alternative name) (522)+COMPOUND OF FORMULA I, Metarhizium        anisopliae var. acridum (scientific name) (523)+COMPOUND OF        FORMULA I, Metarhizium anisopliae var. anisopliae (scientific        name) (523)+COMPOUND OF FORMULA I, Neodiprion sertifer NPV        and N. lecontei NPV (alternative name) (575)+COMPOUND OF FORMULA        I, Orius spp. (alternative name) (596)+COMPOUND OF FORMULA I,        Pasteuria usgae (alternative name)+COMPOUND OF FORMULA I,        Paecilomyces fumosoroseus (alternative name) (613)+COMPOUND OF        FORMULA I, Phytoseiulus persimilis (alternative name)        (644)+COMPOUND OF FORMULA I, Spodoptera exigua multicapsid        nuclear polyhedrosis virus (scientific name) (741)+COMPOUND OF        FORMULA I, Steinernema bibionis (alternative name)        (742)+COMPOUND OF FORMULA I, Steinernema carpocapsae        (alternative name) (742)+COMPOUND OF FORMULA I, Steinernema        feltiae (alternative name) (742)+COMPOUND OF FORMULA I,        Steinernema glaseri (alternative name) (742)+COMPOUND OF FORMULA        I, Steinernema riobrave (alternative name) (742)+COMPOUND OF        FORMULA I, Steinernema riobravis (alternative name)        (742)+COMPOUND OF FORMULA I, Steinernema scapterisci        (alternative name) (742)+COMPOUND OF FORMULA I, Steinernema spp.        (alternative name) (742)+COMPOUND OF FORMULA I, Trichoderma spp.        (alternative name)+COMPOUND OF FORMULA I, Trichogramma spp.        (alternative name) (826)+COMPOUND OF FORMULA I, Typhlodromus        occidentalis (alternative name) (844) and Verticillium lecanii        (alternative name) (848)+COMPOUND OF FORMULA I,    -   a soil sterilant selected from the group of substances        consisting of dimethyl disulfide (IUPAC name)+COMPOUND OF        FORMULA I, iodomethane (IUPAC name) (542) and methyl bromide        (537)+COMPOUND OF FORMULA I,    -   a chemosterilant selected from the group of substances        consisting of apholate [CCN]+COMPOUND OF FORMULA I, bisazir        (alternative name) [CCN]+COMPOUND OF FORMULA I, busulfan        (alternative name) [CCN]+COMPOUND OF FORMULA I, diflubenzuron        (250)+COMPOUND OF FORMULA I, dimatif (alternative name)        [CCN]+COMPOUND OF FORMULA I, hemel [CCN]+COMPOUND OF FORMULA I,        hempa [CCN]+COMPOUND OF FORMULA I, metepa [CCN]+COMPOUND OF        FORMULA I, methiotepa [CCN]+COMPOUND OF FORMULA I, methyl        apholate [CCN]+COMPOUND OF FORMULA I, morzid [CCN]+COMPOUND OF        FORMULA I, penfluoron (alternative name) [CCN]+COMPOUND OF        FORMULA I, tepa [CCN]+COMPOUND OF FORMULA I, thiohempa        (alternative name) [CCN]+COMPOUND OF FORMULA I, thiotepa        (alternative name) [CCN]+COMPOUND OF FORMULA I, tretamine        (alternative name) [CCN] and uredepa (alternative name)        [CCN]+COMPOUND OF FORMULA I,    -   an insect pheromone selected from the group of substances        consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol        (IUPAC name) (222)+COMPOUND OF FORMULA I, (E)-tridec-4-en-1-yl        acetate (IUPAC name) (829)+COMPOUND OF FORMULA I,        (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+COMPOUND OF        FORMULA I, (E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name)        (779)+COMPOUND OF FORMULA I, (Z)-dodec-7-en-1-yl acetate (IUPAC        name) (285)+COMPOUND OF FORMULA I, (Z)-hexadec-1′-enal (IUPAC        name) (436)+COMPOUND OF FORMULA I, (Z)-hexadec-11-en-1-yl        acetate (IUPAC name) (437)+COMPOUND OF FORMULA I,        (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+COMPOUND        OF FORMULA I, (Z)-icos-13-en-10-one (IUPAC name) (448)+COMPOUND        OF FORMULA I, (Z)-tetradec-7-en-1-al (IUPAC name) (782)+COMPOUND        OF FORMULA I, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+COMPOUND        OF FORMULA I, (Z)-tetradec-9-en-1-yl acetate (IUPAC name)        (784)+COMPOUND OF FORMULA I, (7E,9Z)-dodeca-7,9-dien-1-yl        acetate (IUPAC name) (283)+COMPOUND OF FORMULA I,        (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name)        (780)+COMPOUND OF FORMULA I, (9Z,12E)-tetradeca-9,12-dien-1-yl        acetate (IUPAC name) (781)+COMPOUND OF FORMULA I,        14-methyloctadec-1-ene (IUPAC name) (545)+COMPOUND OF FORMULA        1,4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name)        (544)+COMPOUND OF FORMULA I, alpha-multistriatin (alternative        name) [CCN]+COMPOUND OF FORMULA I, brevicomin (alternative name)        [CCN]+COMPOUND OF FORMULA I, codlelure (alternative name)        [CCN]+COMPOUND OF FORMULA I, codlemone (alternative name)        (167)+COMPOUND OF FORMULA I, cuelure (alternative name)        (179)+COMPOUND OF FORMULA I, disparlure (277)+COMPOUND OF        FORMULA I, (E,Z)-7,9-dodecadien-1-yl acetate (IUPAC        name)+COMPOUND OF FORMULA I, dodec-8-en-1-yl acetate (IUPAC        name) (286)+COMPOUND OF FORMULA I, dodec-9-en-1-yl acetate        (IUPAC name) (287)+COMPOUND OF FORMULA I, dodeca-8+COMPOUND OF        FORMULA 1,10-dien-1-yl acetate (IUPAC name) (284)+COMPOUND OF        FORMULA I, dominicalure (alternative name) [CCN]+COMPOUND OF        FORMULA I, ethyl 4-methyloctanoate (IUPAC name) (317)+COMPOUND        OF FORMULA I, eugenol (alternative name) [CCN]+COMPOUND OF        FORMULA I, exosex SPTab (alternative name)+COMPOUND OF FORMULA        I, frontalin (alternative name) [CCN]+COMPOUND OF FORMULA I,        gossyplure (alternative name) (420)+COMPOUND OF FORMULA I,        grandlure (421)+COMPOUND OF FORMULA I, grandlure I (alternative        name) (421)+COMPOUND OF FORMULA I, grandlure II (alternative        name) (421)+COMPOUND OF FORMULA I, grandlure III (alternative        name) (421)+COMPOUND OF FORMULA I, grandlure IV (alternative        name) (421)+COMPOUND OF FORMULA I, hexylure [CCN]+COMPOUND OF        FORMULA I, imicyafos (alternative name) [CCN]+COMPOUND OF        FORMULA I, ipsdienol (alternative name) [CCN]+COMPOUND OF        FORMULA I, ipsenol (alternative name) [CCN]+COMPOUND OF FORMULA        I, japonilure (alternative name) (481)+COMPOUND OF FORMULA I,        lineatin (alternative name) [CCN]+COMPOUND OF FORMULA I, litlure        (alternative name) [CCN]+COMPOUND OF FORMULA I, looplure        (alternative name) [CCN]+COMPOUND OF FORMULA I, medlure        [CCN]+COMPOUND OF FORMULA I, megatomoic acid (alternative name)        [CCN]+COMPOUND OF FORMULA I, methyl eugenol (alternative name)        (540)+COMPOUND OF FORMULA I, muscalure (563)+COMPOUND OF FORMULA        I, octadeca-2,13-dien-1-yl acetate (IUPAC name) (588)+COMPOUND        OF FORMULA I, octadeca-3,13-dien-1-yl acetate (IUPAC name)        (589)+COMPOUND OF FORMULA I, orfralure (alternative name)        [CCN]+COMPOUND OF FORMULA I, oryctalure (alternative name)        (317)+COMPOUND OF FORMULA I, ostramone (alternative name)        [CCN]+COMPOUND OF FORMULA I, siglure [CCN]+COMPOUND OF FORMULA        I, sordidin (alternative name) (736)+COMPOUND OF FORMULA I,        sulcatol (alternative name) [CCN]+COMPOUND OF FORMULA I,        tetradec-11-en-1-yl acetate (IUPAC name) (785)+COMPOUND OF        FORMULA I, trimedlure (839)+COMPOUND OF FORMULA I, trimedlure A        (alternative name) (839)+COMPOUND OF FORMULA I, trimedlure B₁        (alternative name) (839)+COMPOUND OF FORMULA I, trimedlure B₂        (alternative name) (839)+COMPOUND OF FORMULA I, trimedlure C        (alternative name) (839) and trunc-call (alternative name)        [CCN]+COMPOUND OF FORMULA I,    -   an insect repellent selected from the group of substances        consisting of 2-(octylthio)-ethanol (IUPAC name) (591)+COMPOUND        OF FORMULA I, butopyronoxyl (933)+COMPOUND OF FORMULA I,        butoxy(polypropylene glycol) (936)+COMPOUND OF FORMULA I,        dibutyl adipate (IUPAC name) (1046)+COMPOUND OF FORMULA I,        dibutyl phthalate (1047)+COMPOUND OF FORMULA I, dibutyl        succinate (IUPAC name) (1048)+COMPOUND OF FORMULA I,        diethyltoluamide [CCN]+COMPOUND OF FORMULA I, dimethyl carbate        [CCN]+COMPOUND OF FORMULA I, dimethyl phthalate [CCN]+COMPOUND        OF FORMULA I, ethyl hexanediol (1137)+COMPOUND OF FORMULA I,        hexamide [CCN]+COMPOUND OF FORMULA I, methoquin-butyl        (1276)+COMPOUND OF FORMULA I, methylneodecanamide [CCN]+COMPOUND        OF FORMULA I, oxamate [CCN] and picaridin [CCN]+COMPOUND OF        FORMULA I,    -   an insecticide selected from the group of substances consisting        of 1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name)        (1058)+COMPOUND OF FORMULA I,        1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056),        +COMPOUND OF FORMULA 1,1,2-dichloropropane (IUPAC/Chemical        Abstracts name) (1062)+COMPOUND OF FORMULA 1,1,2-dichloropropane        with 1,3-dichloropropene (IUPAC name) (1063)+COMPOUND OF FORMULA        1,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name)        (916)+COMPOUND OF FORMULA        1,2,2,2-trichloro-1-(3,4-dichloro-phenyl)ethyl acetate (IUPAC        name) (1451)+COMPOUND OF FORMULA 1,2,2-dichlorovinyl        2-ethylsulfinylethyl methyl phosphate (IUPAC name)        (1066)+COMPOUND OF FORMULA 1,2-(1,3-dithiolan-2-yl)phenyl        dimethylcarbamate (IUPAC/Chemical Abstracts name)        (1109)+COMPOUND OF FORMULA 1,2-(2-butoxyethoxy)ethyl thiocyanate        (IUPAC/Chemical Abstracts name) (935)+COMPOUND OF FORMULA        1,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate        (IUPAC/Chemical Abstracts name) (1084)+COMPOUND OF FORMULA        1,2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986)+COMPOUND        OF FORMULA 1,2-chlorovinyl diethyl phosphate (IUPAC name)        (984)+COMPOUND OF FORMULA 1,2-imidazolidone (IUPAC name)        (1225)+COMPOUND OF FORMULA 1,2-isovalerylindan-1,3-dione (IUPAC        name) (1246)+COMPOUND OF FORMULA        1,2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name)        (1284)+COMPOUND OF FORMULA 1,2-thiocyanatoethyl laurate (IUPAC        name) (1433)+COMPOUND OF FORMULA 1,3-bromo-1-chloroprop-1-ene        (IUPAC name) (917)+COMPOUND OF FORMULA        1,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name)        (1283)+COMPOUND OF FORMULA        1,4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate (IUPAC        name) (1285)+COMPOUND OF FORMULA I,        5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name)        (1085)+COMPOUND OF FORMULA I, abamectin (1)+COMPOUND OF FORMULA        I, acephate (2)+COMPOUND OF FORMULA I, acetamiprid (4)+COMPOUND        OF FORMULA I, acethion (alternative name) [CCN]+COMPOUND OF        FORMULA I, acetoprole [CCN]+COMPOUND OF FORMULA I, acrinathrin        (9)+COMPOUND OF FORMULA I, acrylonitrile (IUPAC name)        (861)+COMPOUND OF FORMULA I, alanycarb (15)+COMPOUND OF FORMULA        I, aldicarb (16)+COMPOUND OF FORMULA I, aldoxycarb        (863)+COMPOUND OF FORMULA I, aldrin (864)+COMPOUND OF FORMULA I,        allethrin (17)+COMPOUND OF FORMULA I, allosamidin (alternative        name) [CCN]+COMPOUND OF FORMULA I, allyxycarb (866)+COMPOUND OF        FORMULA I, alpha-cypermethrin (202)+COMPOUND OF FORMULA I,        alpha-ecdysone (alternative name) [CCN]+COMPOUND OF FORMULA I,        alpha-endosulfan [CCN]+COMPOUND OF FORMULA I, aluminium        phosphide (640)+COMPOUND OF FORMULA I, amidithion (870)+COMPOUND        OF FORMULA I, amidothioate (872)+COMPOUND OF FORMULA I,        aminocarb (873)+COMPOUND OF FORMULA I, amiton (875)+COMPOUND OF        FORMULA I, amiton hydrogen oxalate (875)+COMPOUND OF FORMULA I,        amitraz (24)+COMPOUND OF FORMULA I, anabasine (877)+COMPOUND OF        FORMULA I, athidathion (883)+COMPOUND OF FORMULA I, AVI 382        (compound code)+COMPOUND OF FORMULA I, AZ 60541 (compound        code)+COMPOUND OF FORMULA I, azadirachtin (alternative name)        (41)+COMPOUND OF FORMULA I, azamethiphos (42)+COMPOUND OF        FORMULA I, azinphos-ethyl (44)+COMPOUND OF FORMULA I,        azinphos-methyl (45)+COMPOUND OF FORMULA I, azothoate        (889)+COMPOUND OF FORMULA I, Bacillus thuringiensis delta        endotoxins (alternative name) (52)+COMPOUND OF FORMULA I, barium        hexafluorosilicate (alternative name) [CCN]+COMPOUND OF FORMULA        I, barium polysulfide (IUPAC/Chemical Abstracts name)        (892)+COMPOUND OF FORMULA I, barthrin [CCN]+COMPOUND OF FORMULA        I, Bayer 22/190 (development code) (893)+COMPOUND OF FORMULA I,        Bayer 22408 (development code) (894)+COMPOUND OF FORMULA I,        bendiocarb (58)+COMPOUND OF FORMULA I, benfuracarb (60)+COMPOUND        OF FORMULA I, bensultap (66)+COMPOUND OF FORMULA I,        beta-cyfluthrin (194)+COMPOUND OF FORMULA I, beta-cypermethrin        (203)+COMPOUND OF FORMULA I, bifenthrin (76)+COMPOUND OF FORMULA        I, bioallethrin (78)+COMPOUND OF FORMULA I, bioallethrin        S-cyclopentenyl isomer (alternative name) (79)+COMPOUND OF        FORMULA I, bioethanomethrin [CCN]+COMPOUND OF FORMULA I,        biopermethrin (908)+COMPOUND OF FORMULA I, bioresmethrin        (80)+COMPOUND OF FORMULA I, bis(2-chloroethyl)ether (IUPAC name)        (909)+COMPOUND OF FORMULA I, bistrifluoron (83)+COMPOUND OF        FORMULA I, borax (86)+COMPOUND OF FORMULA I, brofenvalerate        (alternative name)+COMPOUND OF FORMULA I, bromfenvinfos        (914)+COMPOUND OF FORMULA I, bromocyclen (918)+COMPOUND OF        FORMULA I, bromo-DDT (alternative name) [CCN]+COMPOUND OF        FORMULA I, bromophos (920)+COMPOUND OF FORMULA I,        bromophos-ethyl (921)+COMPOUND OF FORMULA I, bufencarb        (924)+COMPOUND OF FORMULA I, buprofezin (99)+COMPOUND OF FORMULA        I, butacarb (926)+COMPOUND OF FORMULA I, butathiofos        (927)+COMPOUND OF FORMULA I, butocarboxim (103)+COMPOUND OF        FORMULA I, butonate (932)+COMPOUND OF FORMULA I, butoxycarboxim        (104)+COMPOUND OF FORMULA I, butylpyridaben (alternative        name)+COMPOUND OF FORMULA I, cadusafos (109)+COMPOUND OF FORMULA        I, calcium arsenate [CCN]+COMPOUND OF FORMULA I, calcium cyanide        (444)+COMPOUND OF FORMULA I, calcium polysulfide (IUPAC name)        (111)+COMPOUND OF FORMULA I, camphechlor (941)+COMPOUND OF        FORMULA I, carbanolate (943)+COMPOUND OF FORMULA I, carbaryl        (115)+COMPOUND OF FORMULA I, carbofuran (118)+COMPOUND OF        FORMULA I, carbon disulfide (IUPAC/Chemical Abstracts name)        (945)+COMPOUND OF FORMULA I, carbon tetrachloride (IUPAC name)        (946)+COMPOUND OF FORMULA I, carbophenothion (947)+COMPOUND OF        FORMULA I, carbosulfan (119)+COMPOUND OF FORMULA I, cartap        (123)+COMPOUND OF FORMULA I, cartap hydrochloride (123)+COMPOUND        OF FORMULA I, celangulin (alternative name)+COMPOUND OF FORMULA        I, cevadine (alternative name) (725)+COMPOUND OF FORMULA I,        chlorantraniliprole [CCN]+COMPOUND OF FORMULA I, chlorbicyclen        (960)+COMPOUND OF FORMULA I, chlordane (128)+COMPOUND OF FORMULA        I, chlordecone (963)+COMPOUND OF FORMULA I, chlordimeform        (964)+COMPOUND OF FORMULA I, chlordimeform hydrochloride        (964)+COMPOUND OF FORMULA I, chlorethoxyfos (129)+COMPOUND OF        FORMULA I, chlorfenapyr (130)+COMPOUND OF FORMULA I,        chlorfenvinphos (131)+COMPOUND OF FORMULA I, chlorfluazuron        (132)+COMPOUND OF FORMULA I, chlormephos (136)+COMPOUND OF        FORMULA I, chloroform [CCN]+COMPOUND OF FORMULA I, chloropicrin        (141)+COMPOUND OF FORMULA I, chlorphoxim (989)+COMPOUND OF        FORMULA I, chlorprazophos (990)+COMPOUND OF FORMULA I,        chlorpyrifos (145)+COMPOUND OF FORMULA I, chlorpyrifos-methyl        (146)+COMPOUND OF FORMULA I, chlorthiophos (994)+COMPOUND OF        FORMULA I, chromafenozide (150)+COMPOUND OF FORMULA I, cinerin I        (696)+COMPOUND OF FORMULA I, cinerin II (696)+COMPOUND OF        FORMULA I, cinerins (696)+COMPOUND OF FORMULA I, cis-resmethrin        (alternative name)+COMPOUND OF FORMULA I, cismethrin        (80)+COMPOUND OF FORMULA I, clocythrin (alternative        name)+COMPOUND OF FORMULA I, cloethocarb (999)+COMPOUND OF        FORMULA I, closantel (alternative name) [CCN]+COMPOUND OF        FORMULA I, clothianidin (165)+COMPOUND OF FORMULA I, copper        acetoarsenite [CCN]+COMPOUND OF FORMULA I, copper arsenate        [CCN]+COMPOUND OF FORMULA I, copper oleate [CCN]+COMPOUND OF        FORMULA I, coumaphos (174)+COMPOUND OF FORMULA I, coumithoate        (1006)+COMPOUND OF FORMULA I, crotamiton (alternative name)        [CCN]+COMPOUND OF FORMULA I, crotoxyphos (1010)+COMPOUND OF        FORMULA I, crufomate (1011)+COMPOUND OF FORMULA I, cryolite        (alternative name) (177)+COMPOUND OF FORMULA I, CS 708        (development code) (1012)+COMPOUND OF FORMULA I, cyanofenphos        (1019)+COMPOUND OF FORMULA I, cyanophos (184)+COMPOUND OF        FORMULA I, cyanthoate (1020)+COMPOUND OF FORMULA I,        cyantraniliprole [CCN]+COMPOUND OF FORMULA I, cyclethrin        [CCN]+COMPOUND OF FORMULA I, cycloprothrin (188)+COMPOUND OF        FORMULA I, cyfluthrin (193)+COMPOUND OF FORMULA I, cyhalothrin        (196)+COMPOUND OF FORMULA I, cypermethrin (201)+COMPOUND OF        FORMULA I, cyphenothrin (206)+COMPOUND OF FORMULA I, cyromazine        (209)+COMPOUND OF FORMULA I, cythioate (alternative name)        [CCN]+COMPOUND OF FORMULA I, d-limonene (alternative name)        [CCN]+COMPOUND OF FORMULA I, d-tetramethrin (alternative name)        (788)+COMPOUND OF FORMULA I, DAEP (1031)+COMPOUND OF FORMULA I,        dazomet (216)+COMPOUND OF FORMULA I, DDT (219)+COMPOUND OF        FORMULA I, decarbofuran (1034)+COMPOUND OF FORMULA I,        deltamethrin (223)+COMPOUND OF FORMULA I, demephion        (1037)+COMPOUND OF FORMULA I, demephion-O (1037)+COMPOUND OF        FORMULA I, demephion-S (1037)+COMPOUND OF FORMULA I, demeton        (1038)+COMPOUND OF FORMULA I, demeton-methyl (224)+COMPOUND OF        FORMULA I, demeton-O (1038)+COMPOUND OF FORMULA I,        demeton-O-methyl (224)+COMPOUND OF FORMULA I, demeton-S        (1038)+COMPOUND OF FORMULA I, demeton-5-methyl (224)+COMPOUND OF        FORMULA I, demeton-5-methylsulphon (1039)+COMPOUND OF FORMULA I,        diafenthiuron (226)+COMPOUND OF FORMULA I, dialifos        (1042)+COMPOUND OF FORMULA I, diamidafos (1044)+COMPOUND OF        FORMULA I, diazinon (227)+COMPOUND OF FORMULA I, dicapthon        (1050)+COMPOUND OF FORMULA I, dichlofenthion (1051)+COMPOUND OF        FORMULA I, dichlorvos (236)+COMPOUND OF FORMULA I, dicliphos        (alternative name)+COMPOUND OF FORMULA I, dicresyl (alternative        name) [CCN]+COMPOUND OF FORMULA I, dicrotophos (243)+COMPOUND OF        FORMULA I, dicyclanil (244)+COMPOUND OF FORMULA I, dieldrin        (1070)+COMPOUND OF FORMULA I, diethyl 5-methylpyrazol-3-yl        phosphate (IUPAC name) (1076)+COMPOUND OF FORMULA I,        diflubenzuron (250)+COMPOUND OF FORMULA I, dilor (alternative        name) [CCN]+COMPOUND OF FORMULA I, dimefluthrin [CCN]+COMPOUND        OF FORMULA I, dimefox (1081)+COMPOUND OF FORMULA I, dimetan        (1085)+COMPOUND OF FORMULA I, dimethoate (262)+COMPOUND OF        FORMULA I, dimethrin (1083)+COMPOUND OF FORMULA I,        dimethylvinphos (265)+COMPOUND OF FORMULA I, dimetilan        (1086)+COMPOUND OF FORMULA I, dinex (1089)+COMPOUND OF FORMULA        I, dinex-diclexine (1089)+COMPOUND OF FORMULA I, dinoprop        (1093)+COMPOUND OF FORMULA I, dinosam (1094)+COMPOUND OF FORMULA        I, dinoseb (1095)+COMPOUND OF FORMULA I, dinotefuran        (271)+COMPOUND OF FORMULA I, diofenolan (1099)+COMPOUND OF        FORMULA I, dioxabenzofos (1100)+COMPOUND OF FORMULA I, dioxacarb        (1101)+COMPOUND OF FORMULA I, dioxathion (1102)+COMPOUND OF        FORMULA I, disulfoton (278)+COMPOUND OF FORMULA I, dithicrofos        (1108)+COMPOUND OF FORMULA I, DNOC (282)+COMPOUND OF FORMULA I,        doramectin (alternative name) [CCN]+COMPOUND OF FORMULA I, DSP        (1115)+COMPOUND OF FORMULA I, ecdysterone (alternative name)        [CCN]+COMPOUND OF FORMULA I, EI 1642 (development code)        (1118)+COMPOUND OF FORMULA I, emamectin (291)+COMPOUND OF        FORMULA I, emamectin benzoate (291)+COMPOUND OF FORMULA I, EMPC        (1120)+COMPOUND OF FORMULA I, empenthrin (292)+COMPOUND OF        FORMULA I, endosulfan (294)+COMPOUND OF FORMULA I, endothion        (1121)+COMPOUND OF FORMULA I, endrin (1122)+COMPOUND OF FORMULA        I, EPBP (1123)+COMPOUND OF FORMULA I, EPN (297)+COMPOUND OF        FORMULA I, epofenonane (1124)+COMPOUND OF FORMULA I,        eprinomectin (alternative name) [CCN]+COMPOUND OF FORMULA I,        eremophilone oil+COMPOUND OF FORMULA I, esfenvalerate        (302)+COMPOUND OF FORMULA I, etaphos (alternative name)        [CCN]+COMPOUND OF FORMULA I, ethiofencarb (308)+COMPOUND OF        FORMULA I, ethion (309)+COMPOUND OF FORMULA I, ethiprole        (310)+COMPOUND OF FORMULA I, ethoate-methyl (1134)+COMPOUND OF        FORMULA I, ethoprophos (312)+COMPOUND OF FORMULA I, ethyl        formate (IUPAC name) [CCN]+COMPOUND OF FORMULA I, ethyl-DDD        (alternative name) (1056)+COMPOUND OF FORMULA I, ethylene        dibromide (316)+COMPOUND OF FORMULA I, ethylene dichloride        (chemical name) (1136)+COMPOUND OF FORMULA I, ethylene oxide        [CCN]+COMPOUND OF FORMULA I, etofenprox (319)+COMPOUND OF        FORMULA I, etrimfos (1142)+COMPOUND OF FORMULA I, EXD        (1143)+COMPOUND OF FORMULA I, famphur (323)+COMPOUND OF FORMULA        I, fenamiphos (326)+COMPOUND OF FORMULA I, fenazaflor        (1147)+COMPOUND OF FORMULA I, fenchlorphos (1148)+COMPOUND OF        FORMULA I, fenethacarb (1149)+COMPOUND OF FORMULA I, fenfluthrin        (1150)+COMPOUND OF FORMULA I, fenitrothion (335)+COMPOUND OF        FORMULA I, fenobucarb (336)+COMPOUND OF FORMULA I, fenoxacrim        (1153)+COMPOUND OF FORMULA I, fenoxycarb (340)+COMPOUND OF        FORMULA I, fenpirithrin (1155)+COMPOUND OF FORMULA I,        fenpropathrin (342)+COMPOUND OF FORMULA I, fenpyrad (alternative        name)+COMPOUND OF FORMULA I, fensulfothion (1158)+COMPOUND OF        FORMULA I, fenthion (346)+COMPOUND OF FORMULA I, fenthion-ethyl        [CCN]+COMPOUND OF FORMULA I, fenvalerate (349)+COMPOUND OF        FORMULA I, fipronil (354)+COMPOUND OF FORMULA I, flometoquin        [CCN]+COMPOUND OF FORMULA I, flonicamid (358)+COMPOUND OF        FORMULA I, flubendiamide (CAS. Reg. No.: 272451-65-7)+COMPOUND        OF FORMULA I, flucofuron (1168)+COMPOUND OF FORMULA I,        flucycloxuron (366)+COMPOUND OF FORMULA I, flucythrinate        (367)+COMPOUND OF FORMULA I, fluenetil (1169)+COMPOUND OF        FORMULA I, fluensulfon [CCN]+COMPOUND OF FORMULA I, flufenerim        [CCN]+COMPOUND OF FORMULA I, flufenoxuron (370)+COMPOUND OF        FORMULA I, flufenprox (1171)+COMPOUND OF FORMULA I, flufiprole        [CCN]+COMPOUND OF FORMULA I, flumethrin (372)+COMPOUND OF        FORMULA I, flupyradifurone [CCN]+COMPOUND OF FORMULA I,        fluvalinate (1184)+COMPOUND OF FORMULA I, FMC 1137 (development        code) (1185)+COMPOUND OF FORMULA I, fonofos (1191)+COMPOUND OF        FORMULA I, formetanate (405)+COMPOUND OF FORMULA I, formetanate        hydrochloride (405)+COMPOUND OF FORMULA I, formothion        (1192)+COMPOUND OF FORMULA I, formparanate (1193)+COMPOUND OF        FORMULA I, fosmethilan (1194)+COMPOUND OF FORMULA I, fospirate        (1195)+COMPOUND OF FORMULA I, fosthiazate (408)+COMPOUND OF        FORMULA I, fosthietan (1196)+COMPOUND OF FORMULA I, furathiocarb        (412)+COMPOUND OF FORMULA I, furethrin (1200)+COMPOUND OF        FORMULA I, gamma-cyhalothrin (197)+COMPOUND OF FORMULA I,        gamma-HCH (430)+COMPOUND OF FORMULA I, guazatine (422)+COMPOUND        OF FORMULA I, guazatine acetates (422)+COMPOUND OF FORMULA I,        GY-81 (development code) (423)+COMPOUND OF FORMULA I, halfenprox        (424)+COMPOUND OF FORMULA I, halofenozide (425)+COMPOUND OF        FORMULA I, HCH (430)+COMPOUND OF FORMULA I, HEOD (1070)+COMPOUND        OF FORMULA I, heptachlor (1211)+COMPOUND OF FORMULA I,        heptenophos (432)+COMPOUND OF FORMULA I, heterophos        [CCN]+COMPOUND OF FORMULA I, hexaflumuron (439)+COMPOUND OF        FORMULA I, HHDN (864)+COMPOUND OF FORMULA I, hydramethylnon        (443)+COMPOUND OF FORMULA I, hydrogen cyanide (444)+COMPOUND OF        FORMULA I, hydroprene (445)+COMPOUND OF FORMULA I, hyquincarb        (1223)+COMPOUND OF FORMULA I, imidacloprid (458)+COMPOUND OF        FORMULA I, imiprothrin (460)+COMPOUND OF FORMULA I, indoxacarb        (465)+COMPOUND OF FORMULA I, iodomethane (IUPAC name)        (542)+COMPOUND OF FORMULA I, IPPA-152004 (compound        code)+COMPOUND OF FORMULA I, IPSP (1229)+COMPOUND OF FORMULA I,        isazofos (1231)+COMPOUND OF FORMULA I, isobenzan (1232)+COMPOUND        OF FORMULA I, isocarbophos (alternative name) (473)+COMPOUND OF        FORMULA I, isodrin (1235)+COMPOUND OF FORMULA I, isofenphos        (1236)+COMPOUND OF FORMULA I, isolane (1237)+COMPOUND OF FORMULA        I, isoprocarb (472)+COMPOUND OF FORMULA I, isopropyl        O-(methoxyaminothiophosphoryl)salicylate (IUPAC name)        (473)+COMPOUND OF FORMULA I, isoprothiolane (474)+COMPOUND OF        FORMULA I, isothioate (1244)+COMPOUND OF FORMULA I, isoxathion        (480)+COMPOUND OF FORMULA I, ivermectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, jasmolin I (696)+COMPOUND OF        FORMULA I, jasmolin II (696)+COMPOUND OF FORMULA I, jodfenphos        (1248)+COMPOUND OF FORMULA I, juvenile hormone I (alternative        name) [CCN]+COMPOUND OF FORMULA I, juvenile hormone II        (alternative name) [CCN]+COMPOUND OF FORMULA I, juvenile hormone        III (alternative name) [CCN]+COMPOUND OF FORMULA I, kelevan        (1249)+COMPOUND OF FORMULA I, kinoprene (484)+COMPOUND OF        FORMULA I, lambda-cyhalothrin (198)+COMPOUND OF FORMULA I, lead        arsenate [CCN]+COMPOUND OF FORMULA I, lepimectin (CCN)+COMPOUND        OF FORMULA I, leptophos (1250)+COMPOUND OF FORMULA I, lindane        (430)+COMPOUND OF FORMULA I, lirimfos (1251)+COMPOUND OF FORMULA        I, lufenuron (490)+COMPOUND OF FORMULA I, lythidathion        (1253)+COMPOUND OF FORMULA I, m-cumenyl methylcarbamate (IUPAC        name) (1014)+COMPOUND OF FORMULA I, magnesium phosphide (IUPAC        name) (640)+COMPOUND OF FORMULA I, malathion (492)+COMPOUND OF        FORMULA I, malonoben (1254)+COMPOUND OF FORMULA I, mazidox        (1255)+COMPOUND OF FORMULA I, mecarbam (502)+COMPOUND OF FORMULA        I, mecarphon (1258)+COMPOUND OF FORMULA I, menazon        (1260)+COMPOUND OF FORMULA I, mephosfolan (1261)+COMPOUND OF        FORMULA I, mercurous chloride (513)+COMPOUND OF FORMULA I,        mesulfenfos (1263)+COMPOUND OF FORMULA I, metaflumizone        (CCN)+COMPOUND OF FORMULA I, metam (519)+COMPOUND OF FORMULA I,        metam-potassium (alternative name) (519)+COMPOUND OF FORMULA I,        metam-sodium (519)+COMPOUND OF FORMULA I, methacrifos        (1266)+COMPOUND OF FORMULA I, methamidophos (527)+COMPOUND OF        FORMULA I, methanesulfonyl fluoride (IUPAC/Chemical Abstracts        name) (1268)+COMPOUND OF FORMULA I, methidathion (529)+COMPOUND        OF FORMULA I, methiocarb (530)+COMPOUND OF FORMULA I,        methocrotophos (1273)+COMPOUND OF FORMULA I, methomyl        (531)+COMPOUND OF FORMULA I, methoprene (532)+COMPOUND OF        FORMULA I, methoquin-butyl (1276)+COMPOUND OF FORMULA I,        methothrin (alternative name) (533)+COMPOUND OF FORMULA I,        methoxychlor (534)+COMPOUND OF FORMULA I, methoxyfenozide        (535)+COMPOUND OF FORMULA I, methyl bromide (537)+COMPOUND OF        FORMULA I, methyl isothiocyanate (543)+COMPOUND OF FORMULA I,        methylchloroform (alternative name) [CCN]+COMPOUND OF FORMULA I,        methylene chloride [CCN]+COMPOUND OF FORMULA I, metofluthrin        [CCN]+COMPOUND OF FORMULA I, metolcarb (550)+COMPOUND OF FORMULA        I, metoxadiazone (1288)+COMPOUND OF FORMULA I, mevinphos        (556)+COMPOUND OF FORMULA I, mexacarbate (1290)+COMPOUND OF        FORMULA I, milbemectin (557)+COMPOUND OF FORMULA I, milbemycin        oxime (alternative name) [CCN]+COMPOUND OF FORMULA I, mipafox        (1293)+COMPOUND OF FORMULA I, mirex (1294)+COMPOUND OF FORMULA        I, monocrotophos (561)+COMPOUND OF FORMULA I, morphothion        (1300)+COMPOUND OF FORMULA I, moxidectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, naftalofos (alternative name)        [CCN]+COMPOUND OF FORMULA I, naled (567)+COMPOUND OF FORMULA I,        naphthalene (IUPAC/Chemical Abstracts name) (1303)+COMPOUND OF        FORMULA I, NC-170 (development code) (1306)+COMPOUND OF FORMULA        I, NC-184 (compound code)+COMPOUND OF FORMULA I, nicotine        (578)+COMPOUND OF FORMULA I, nicotine sulfate (578)+COMPOUND OF        FORMULA I, nifluridide (1309)+COMPOUND OF FORMULA I, nitenpyram        (579)+COMPOUND OF FORMULA I, nithiazine (1311)+COMPOUND OF        FORMULA I, nitrilacarb (1313)+COMPOUND OF FORMULA I, nitrilacarb        1:1 zinc chloride complex (1313)+COMPOUND OF FORMULA I, NNI-0101        (compound code)+COMPOUND OF FORMULA I, NNI-0250 (compound        code)+COMPOUND OF FORMULA I, nornicotine (traditional name)        (1319)+COMPOUND OF FORMULA I, novaluron (585)+COMPOUND OF        FORMULA I, noviflumuron (586)+COMPOUND OF FORMULA 1,        O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC        name) (1057)+COMPOUND OF FORMULA I, O,O-diethyl        O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)        (1074)+COMPOUND OF FORMULA I, O,O-diethyl        O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name)        (1075)+COMPOUND OF FORMULA I, O,O,O′,O′-tetrapropyl        dithiopyrophosphate (IUPAC name) (1424)+COMPOUND OF FORMULA I,        oleic acid (IUPAC name) (593)+COMPOUND OF FORMULA I, omethoate        (594)+COMPOUND OF FORMULA I, oxamyl (602)+COMPOUND OF FORMULA I,        oxydemeton-methyl (609)+COMPOUND OF FORMULA I, oxydeprofos        (1324)+COMPOUND OF FORMULA I, oxydisulfoton (1325)+COMPOUND OF        FORMULA I, pp′-DDT (219)+COMPOUND OF FORMULA I,        para-dichlorobenzene [CCN]+COMPOUND OF FORMULA I, parathion        (615)+COMPOUND OF FORMULA I, parathion-methyl (616)+COMPOUND OF        FORMULA I, penfluoron (alternative name) [CCN]+COMPOUND OF        FORMULA I, pentachlorophenol (623)+COMPOUND OF FORMULA I,        pentachlorophenyl laurate (IUPAC name) (623)+COMPOUND OF FORMULA        I, permethrin (626)+COMPOUND OF FORMULA I, petroleum oils        (alternative name) (628)+COMPOUND OF FORMULA I, PH 60-38        (development code) (1328)+COMPOUND OF FORMULA I, phenkapton        (1330)+COMPOUND OF FORMULA I, phenothrin (630)+COMPOUND OF        FORMULA I, phenthoate (631)+COMPOUND OF FORMULA I, phorate        (636)+COMPOUND OF FORMULA I, phosalone (637)+COMPOUND OF FORMULA        I, phosfolan (1338)+COMPOUND OF FORMULA I, phosmet        (638)+COMPOUND OF FORMULA I, phosnichlor (1339)+COMPOUND OF        FORMULA I, phosphamidon (639)+COMPOUND OF FORMULA I, phosphine        (IUPAC name) (640)+COMPOUND OF FORMULA I, phoxim (642)+COMPOUND        OF FORMULA I, phoxim-methyl (1340)+COMPOUND OF FORMULA I,        pirimetaphos (1344)+COMPOUND OF FORMULA I, pirimicarb        (651)+COMPOUND OF FORMULA I, pirimiphos-ethyl (1345)+COMPOUND OF        FORMULA I, pirimiphos-methyl (652)+COMPOUND OF FORMULA I,        polychlorodicyclopentadiene isomers (IUPAC name) (1346)+COMPOUND        OF FORMULA I, polychloroterpenes (traditional name)        (1347)+COMPOUND OF FORMULA I, potassium arsenite [CCN]+COMPOUND        OF FORMULA I, potassium thiocyanate [CCN]+COMPOUND OF FORMULA I,        prallethrin (655)+COMPOUND OF FORMULA I, precocene I        (alternative name) [CCN]+COMPOUND OF FORMULA I, precocene II        (alternative name) [CCN]+COMPOUND OF FORMULA I, precocene III        (alternative name) [CCN]+COMPOUND OF FORMULA I, primidophos        (1349)+COMPOUND OF FORMULA I, profenofos (662)+COMPOUND OF        FORMULA I, profluthrin [CCN]+COMPOUND OF FORMULA I, promacyl        (1354)+COMPOUND OF FORMULA I, promecarb (1355)+COMPOUND OF        FORMULA I, propaphos (1356)+COMPOUND OF FORMULA I, propetamphos        (673)+COMPOUND OF FORMULA I, propoxur (678)+COMPOUND OF FORMULA        I, prothidathion (1360)+COMPOUND OF FORMULA I, prothiofos        (686)+COMPOUND OF FORMULA I, prothoate (1362)+COMPOUND OF        FORMULA I, protrifenbute [CCN]+COMPOUND OF FORMULA I,        pymetrozine (688)+COMPOUND OF FORMULA I, pyraclofos        (689)+COMPOUND OF FORMULA I, pyrafluprole [CCN]+COMPOUND OF        FORMULA I, pyrazophos (693)+COMPOUND OF FORMULA I, pyresmethrin        (1367)+COMPOUND OF FORMULA I, pyrethrin I (696)+COMPOUND OF        FORMULA I, pyrethrin II (696)+COMPOUND OF FORMULA I, pyrethrins        (696)+COMPOUND OF FORMULA I, pyridaben (699)+COMPOUND OF FORMULA        I, pyridalyl (700)+COMPOUND OF FORMULA I, pyridaphenthion        (701)+COMPOUND OF FORMULA I, pyrifluquinazon [CCN]+COMPOUND OF        FORMULA I, pyrimidifen (706)+COMPOUND OF FORMULA I, pyrimitate        (1370)+COMPOUND OF FORMULA I, pyriprole [CCN]+COMPOUND OF        FORMULA I, pyriproxyfen (708)+COMPOUND OF FORMULA I, quassia        (alternative name) [CCN]+COMPOUND OF FORMULA I, quinalphos        (711)+COMPOUND OF FORMULA I, quinalphos-methyl (1376)+COMPOUND        OF FORMULA I, quinothion (1380)+COMPOUND OF FORMULA I,        quintiofos (1381)+COMPOUND OF FORMULA I, R-1492 (development        code) (1382)+COMPOUND OF FORMULA I, rafoxanide (alternative        name) [CCN]+COMPOUND OF FORMULA I, resmethrin (719)+COMPOUND OF        FORMULA I, rotenone (722)+COMPOUND OF FORMULA I, RU 15525        (development code) (723)+COMPOUND OF FORMULA I, RU 25475        (development code) (1386)+COMPOUND OF FORMULA I, ryania        (alternative name) (1387)+COMPOUND OF FORMULA I, ryanodine        (traditional name) (1387)+COMPOUND OF FORMULA I, sabadilla        (alternative name) (725)+COMPOUND OF FORMULA I, schradan        (1389)+COMPOUND OF FORMULA I, sebufos (alternative        name)+COMPOUND OF FORMULA I, selamectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, SI-0009 (compound code)+COMPOUND OF        FORMULA I, SI-0205 (compound code)+COMPOUND OF FORMULA I,        SI-0404 (compound code)+COMPOUND OF FORMULA I, SI-0405 (compound        code)+COMPOUND OF FORMULA I, silafluofen (728)+COMPOUND OF        FORMULA I, SN 72129 (development code) (1397)+COMPOUND OF        FORMULA I, sodium arsenite [CCN]+COMPOUND OF FORMULA I, sodium        cyanide (444)+COMPOUND OF FORMULA I, sodium fluoride        (IUPAC/Chemical Abstracts name) (1399)+COMPOUND OF FORMULA I,        sodium hexafluorosilicate (1400)+COMPOUND OF FORMULA I, sodium        pentachlorophenoxide (623)+COMPOUND OF FORMULA I, sodium        selenate (IUPAC name) (1401)+COMPOUND OF FORMULA I, sodium        thiocyanate [CCN]+COMPOUND OF FORMULA I, sophamide        (1402)+COMPOUND OF FORMULA I, spinetoram [CCN]+COMPOUND OF        FORMULA I, spinosad (737)+COMPOUND OF FORMULA I, spiromesifen        (739)+COMPOUND OF FORMULA I, spirotetramat [CCN]+COMPOUND OF        FORMULA I, sulcofuron (746)+COMPOUND OF FORMULA I,        sulcofuron-sodium (746)+COMPOUND OF FORMULA I, sulfluramid        (750)+COMPOUND OF FORMULA I, sulfotep (753)+COMPOUND OF FORMULA        I, sulfoxaflor [CCN]+COMPOUND OF FORMULA I, sulfuryl fluoride        (756)+COMPOUND OF FORMULA I, sulprofos (1408)+COMPOUND OF        FORMULA I, tar oils (alternative name) (758)+COMPOUND OF FORMULA        I, tau-fluvalinate (398)+COMPOUND OF FORMULA I, tazimcarb        (1412)+COMPOUND OF FORMULA I, TDE (1414)+COMPOUND OF FORMULA I,        tebufenozide (762)+COMPOUND OF FORMULA I, tebufenpyrad        (763)+COMPOUND OF FORMULA I, tebupirimfos (764)+COMPOUND OF        FORMULA I, teflubenzuron (768)+COMPOUND OF FORMULA I, tefluthrin        (769)+COMPOUND OF FORMULA I, temephos (770)+COMPOUND OF FORMULA        I, TEPP (1417)+COMPOUND OF FORMULA I, terallethrin        (1418)+COMPOUND OF FORMULA I, terbam (alternative name)+COMPOUND        OF FORMULA I, terbufos (773)+COMPOUND OF FORMULA I,        tetrachloroethane [CCN]+COMPOUND OF FORMULA I, tetrachlorvinphos        (777)+COMPOUND OF FORMULA I, tetramethrin (787)+COMPOUND OF        FORMULA I, tetramethylfluthrin (CAS. Reg. No.:        84937-88-2)+COMPOUND OF FORMULA I, theta-cypermethrin        (204)+COMPOUND OF FORMULA I, thiacloprid (791)+COMPOUND OF        FORMULA I, thiafenox (alternative name)+COMPOUND OF FORMULA I,        thiamethoxam (792)+COMPOUND OF FORMULA I, thicrofos        (1428)+COMPOUND OF FORMULA I, thiocarboxime (1431)+COMPOUND OF        FORMULA I, thiocyclam (798)+COMPOUND OF FORMULA I, thiocyclam        hydrogen oxalate (798)+COMPOUND OF FORMULA I, thiodicarb        (799)+COMPOUND OF FORMULA I, thiofanox (800)+COMPOUND OF FORMULA        I, thiometon (801)+COMPOUND OF FORMULA I, thionazin        (1434)+COMPOUND OF FORMULA I, thiosultap (803)+COMPOUND OF        FORMULA I, thiosultap-sodium (803)+COMPOUND OF FORMULA I,        thuringiensin (alternative name) [CCN]+COMPOUND OF FORMULA I,        tolfenpyrad (809)+COMPOUND OF FORMULA I, tralomethrin        (812)+COMPOUND OF FORMULA I, transfluthrin (813)+COMPOUND OF        FORMULA I, transpermethrin (1440)+COMPOUND OF FORMULA I,        triamiphos (1441)+COMPOUND OF FORMULA I, triazamate        (818)+COMPOUND OF FORMULA I, triazophos (820)+COMPOUND OF        FORMULA I, triazuron (alternative name)+COMPOUND OF FORMULA I,        trichlorfon (824)+COMPOUND OF FORMULA I, trichlormetaphos-3        (alternative name) [CCN]+COMPOUND OF FORMULA I, trichloronat        (1452)+COMPOUND OF FORMULA I, trifenofos (1455)+COMPOUND OF        FORMULA I, triflumuron (835)+COMPOUND OF FORMULA I, trimethacarb        (840)+COMPOUND OF FORMULA I, triprene (1459)+COMPOUND OF FORMULA        I, vamidothion (847)+COMPOUND OF FORMULA I, vaniliprole        [CCN]+COMPOUND OF FORMULA I, veratridine (alternative name)        (725)+COMPOUND OF FORMULA I, veratrine (alternative name)        (725)+COMPOUND OF FORMULA I, XMC (853)+COMPOUND OF FORMULA I,        xylylcarb (854)+COMPOUND OF FORMULA I, yl-5302 (compound        code)+COMPOUND OF FORMULA I, zeta-cypermethrin (205)+COMPOUND OF        FORMULA I, zetamethrin (alternative name)+COMPOUND OF FORMULA I,        zinc phosphide (640)+COMPOUND OF FORMULA I, zolaprofos (1469),        ZJ0967 (development code)+COMPOUND OF FORMULA I, ZJ3757        (development code)+COMPOUND OF FORMULA I, and ZXI 8901        (development code) (858)+COMPOUND OF FORMULA I,    -   a molluscicide selected from the group of substances consisting        of bis(tributyltin) oxide (IUPAC name) (913)+COMPOUND OF FORMULA        I, bromoacetamide [CCN]+COMPOUND OF FORMULA I, calcium arsenate        [CCN]+COMPOUND OF FORMULA I, cloethocarb (999)+COMPOUND OF        FORMULA I, copper acetoarsenite [CCN]+COMPOUND OF FORMULA I,        copper sulfate (172)+COMPOUND OF FORMULA I, fentin        (347)+COMPOUND OF FORMULA I, ferric phosphate (IUPAC name)        (352)+COMPOUND OF FORMULA I, metaldehyde (518)+COMPOUND OF        FORMULA I, methiocarb (530)+COMPOUND OF FORMULA I, niclosamide        (576)+COMPOUND OF FORMULA I, niclosamide-olamine (576)+COMPOUND        OF FORMULA I, pentachlorophenol (623)+COMPOUND OF FORMULA I,        sodium pentachlorophenoxide (623)+COMPOUND OF FORMULA I,        tazimcarb (1412)+COMPOUND OF FORMULA I, thiodicarb        (799)+COMPOUND OF FORMULA I, tralopyril [CCN]+COMPOUND OF        FORMULA I, tributyltin oxide (913)+COMPOUND OF FORMULA I,        trifenmorph (1454)+COMPOUND OF FORMULA I, trimethacarb        (840)+COMPOUND OF FORMULA I, triphenyltin acetate (IUPAC        name) (347) and triphenyltin hydroxide (IUPAC name)        (347)+COMPOUND OF FORMULA I,    -   a nematicide selected from the group of substances consisting of        AKD-3088 (compound code)+COMPOUND OF FORMULA        1,1,2-dibromo-3-chloropropane (I UPAC/Chemical Abstracts name)        (1045)+COMPOUND OF FORMULA 1,1,2-dichloropropane (IUPAC/Chemical        Abstracts name) (1062)+COMPOUND OF FORMULA 1,1,2-dichloropropane        with 1,3-dichloropropene (IUPAC name) (1063)+COMPOUND OF FORMULA        1,1,3-dichloropropene (233)+COMPOUND OF FORMULA        1,3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical        Abstracts name) (1065)+COMPOUND OF FORMULA        1,3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name)        (980)+COMPOUND OF FORMULA        1,5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC        name) (1286)+COMPOUND OF FORMULA 1,6-isopentenylaminopurine        (alternative name) (210)+COMPOUND OF FORMULA I, abamectin        (1)+COMPOUND OF FORMULA I, acetoprole [CCN]+COMPOUND OF FORMULA        I, alanycarb (15)+COMPOUND OF FORMULA I, aldicarb (16)+COMPOUND        OF FORMULA I, aldoxycarb (863)+COMPOUND OF FORMULA I, AZ 60541        (compound code)+COMPOUND OF FORMULA I, benclothiaz        [CCN]+COMPOUND OF FORMULA I, benomyl (62)+COMPOUND OF FORMULA I,        butylpyridaben (alternative name)+COMPOUND OF FORMULA I,        cadusafos (109)+COMPOUND OF FORMULA I, carbofuran (118)+COMPOUND        OF FORMULA I, carbon disulfide (945)+COMPOUND OF FORMULA I,        carbosulfan (119)+COMPOUND OF FORMULA I, chloropicrin        (141)+COMPOUND OF FORMULA I, chlorpyrifos (145)+COMPOUND OF        FORMULA I, cloethocarb (999)+COMPOUND OF FORMULA I, cytokinins        (alternative name) (210)+COMPOUND OF FORMULA I, dazomet        (216)+COMPOUND OF FORMULA I, DBCP (1045)+COMPOUND OF FORMULA I,        DCIP (218)+COMPOUND OF FORMULA I, diamidafos (1044)+COMPOUND OF        FORMULA I, dichlofenthion (1051)+COMPOUND OF FORMULA I,        dicliphos (alternative name)+COMPOUND OF FORMULA I, dimethoate        (262)+COMPOUND OF FORMULA I, doramectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, emamectin (291)+COMPOUND OF FORMULA        I, emamectin benzoate (291)+COMPOUND OF FORMULA I, eprinomectin        (alternative name) [CCN]+COMPOUND OF FORMULA I, ethoprophos        (312)+COMPOUND OF FORMULA I, ethylene dibromide (316)+COMPOUND        OF FORMULA I, fenamiphos (326)+COMPOUND OF FORMULA I, fenpyrad        (alternative name)+COMPOUND OF FORMULA I, fensulfothion        (1158)+COMPOUND OF FORMULA I, fluensulfone (CAS. Reg. No.:        318290-98-1)+COMPOUND OF FORMULA I, fosthiazate (408)+COMPOUND        OF FORMULA I, fosthietan (1196)+COMPOUND OF FORMULA I, furfural        (alternative name) [CCN]+COMPOUND OF FORMULA I, GY-81        (development code) (423)+COMPOUND OF FORMULA I, heterophos        [CCN]+COMPOUND OF FORMULA I, imicyafos [CCN]+COMPOUND OF FORMULA        I, imicyafos (alternative name) [CCN]+COMPOUND OF FORMULA I,        iodomethane (IUPAC name) (542)+COMPOUND OF FORMULA I, isamidofos        (1230)+COMPOUND OF FORMULA I, isazofos (1231)+COMPOUND OF        FORMULA I, ivermectin (alternative name) [CCN]+COMPOUND OF        FORMULA I, kinetin (alternative name) (210)+COMPOUND OF FORMULA        I, mecarphon (1258)+COMPOUND OF FORMULA I, metam (519)+COMPOUND        OF FORMULA I, metam-potassium (alternative name) (519)+COMPOUND        OF FORMULA I, metam-sodium (519)+COMPOUND OF FORMULA I, methyl        bromide (537)+COMPOUND OF FORMULA I, methyl isothiocyanate        (543)+COMPOUND OF FORMULA I, milbemycin oxime (alternative name)        [CCN]+COMPOUND OF FORMULA I, moxidectin (alternative name)        [CCN]+COMPOUND OF FORMULA I, Myrothecium verrucaria composition        (alternative name) (565)+COMPOUND OF FORMULA I, NC-184 (compound        code)+COMPOUND OF FORMULA I, oxamyl (602)+COMPOUND OF FORMULA I,        phorate (636)+COMPOUND OF FORMULA I, phosphamidon (639)+COMPOUND        OF FORMULA I, phosphocarb [CCN]+COMPOUND OF FORMULA I, sebufos        (alternative name)+COMPOUND OF FORMULA I, selamectin        (alternative name) [CCN]+COMPOUND OF FORMULA I, spinosad        (737)+COMPOUND OF FORMULA I, terbam (alternative name)+COMPOUND        OF FORMULA I, terbufos (773)+COMPOUND OF FORMULA I,        tetrachlorothiophene (IUPAC/Chemical Abstracts name)        (1422)+COMPOUND OF FORMULA I, thiafenox (alternative        name)+COMPOUND OF FORMULA I, thionazin (1434)+COMPOUND OF        FORMULA I, triazophos (820)+COMPOUND OF FORMULA I, triazuron        (alternative name)+COMPOUND OF FORMULA I, xylenols        [CCN]+COMPOUND OF FORMULA I, YI-5302 (compound code) and zeatin        (alternative name) (210)+COMPOUND OF FORMULA I,    -   a nitrification inhibitor selected from the group of substances        consisting of potassium ethylxanthate [CCN] and nitrapyrin        (580)+COMPOUND OF FORMULA I,    -   a plant activator selected from the group of substances        consisting of acibenzolar (6)+COMPOUND OF FORMULA I,        acibenzolar-5-methyl (6)+COMPOUND OF FORMULA I,        probenazole (658) and Reynoutria sachalinensis extract        (alternative name) (720)+COMPOUND OF FORMULA I,    -   a rodenticide selected from the group of substances consisting        of 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+COMPOUND OF        FORMULA 1,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC        name) (748)+COMPOUND OF FORMULA I, alpha-chlorohydrin        [CCN]+COMPOUND OF FORMULA I, aluminium phosphide (640)+COMPOUND        OF FORMULA I, antu (880)+COMPOUND OF FORMULA I, arsenous oxide        (882)+COMPOUND OF FORMULA I, barium carbonate (891)+COMPOUND OF        FORMULA I, bisthiosemi (912)+COMPOUND OF FORMULA I, brodifacoum        (89)+COMPOUND OF FORMULA I, bromadiolone (91)+COMPOUND OF        FORMULA I, bromethalin (92)+COMPOUND OF FORMULA I, calcium        cyanide (444)+COMPOUND OF FORMULA I, chloralose (127)+COMPOUND        OF FORMULA I, chlorophacinone (140)+COMPOUND OF FORMULA I,        cholecalciferol (alternative name) (850)+COMPOUND OF FORMULA I,        coumachlor (1004)+COMPOUND OF FORMULA I, coumafuryl        (1005)+COMPOUND OF FORMULA I, coumatetralyl (175)+COMPOUND OF        FORMULA I, crimidine (1009)+COMPOUND OF FORMULA I, difenacoum        (246)+COMPOUND OF FORMULA I, difethialone (249)+COMPOUND OF        FORMULA I, diphacinone (273)+COMPOUND OF FORMULA I,        ergocalciferol (301)+COMPOUND OF FORMULA I, flocoumafen        (357)+COMPOUND OF FORMULA I, fluoroacetamide (379)+COMPOUND OF        FORMULA I, flupropadine (1183)+COMPOUND OF FORMULA I,        flupropadine hydrochloride (1183)+COMPOUND OF FORMULA I,        gamma-HCH (430)+COMPOUND OF FORMULA I, HCH (430)+COMPOUND OF        FORMULA I, hydrogen cyanide (444)+COMPOUND OF FORMULA I,        iodomethane (IUPAC name) (542)+COMPOUND OF FORMULA I, lindane        (430)+COMPOUND OF FORMULA I, magnesium phosphide (IUPAC name)        (640)+COMPOUND OF FORMULA I, methyl bromide (537)+COMPOUND OF        FORMULA I, norbormide (1318)+COMPOUND OF FORMULA I, phosacetim        (1336)+COMPOUND OF FORMULA I, phosphine (IUPAC name)        (640)+COMPOUND OF FORMULA I, phosphorus [CCN]+COMPOUND OF        FORMULA I, pindone (1341)+COMPOUND OF FORMULA I, potassium        arsenite [CCN]+COMPOUND OF FORMULA I, pyrinuron (1371)+COMPOUND        OF FORMULA I, scilliroside (1390)+COMPOUND OF FORMULA I, sodium        arsenite [CCN]+COMPOUND OF FORMULA I, sodium cyanide        (444)+COMPOUND OF FORMULA I, sodium fluoro-acetate        (735)+COMPOUND OF FORMULA I, strychnine (745)+COMPOUND OF        FORMULA I, thallium sulfate [CCN]+COMPOUND OF FORMULA I,        warfarin (851) and zinc phosphide (640)+COMPOUND OF FORMULA I,    -   a synergist selected from the group of substances consisting of        2-(2-butoxyethoxy)-ethyl piperonylate (IUPAC name)        (934)+COMPOUND OF FORMULA I,        5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name)        (903)+COMPOUND OF FORMULA I, farnesol with nerolidol        (alternative name) (324)+COMPOUND OF FORMULA I, MB-599        (development code) (498)+COMPOUND OF FORMULA I, MGK 264        (development code) (296)+COMPOUND OF FORMULA I, piperonyl        butoxide (649)+COMPOUND OF FORMULA I, piprotal (1343)+COMPOUND        OF FORMULA I, propyl isomer (1358)+COMPOUND OF FORMULA I, S421        (development code) (724)+COMPOUND OF FORMULA I, sesamex        (1393)+COMPOUND OF FORMULA I, sesasmolin (1394) and sulfoxide        (1406)+COMPOUND OF FORMULA I,    -   an animal repellent selected from the group of substances        consisting of anthraquinone (32)+COMPOUND OF FORMULA I,        chloralose (127)+COMPOUND OF FORMULA I, copper naphthenate        [CCN]+COMPOUND OF FORMULA I, copper oxychloride (171)+COMPOUND        OF FORMULA I, diazinon (227)+COMPOUND OF FORMULA I,        dicyclopentadiene (chemical name) (1069)+COMPOUND OF FORMULA I,        guazatine (422)+COMPOUND OF FORMULA I, guazatine acetates        (422)+COMPOUND OF FORMULA I, methiocarb (530)+COMPOUND OF        FORMULA I, pyridin-4-amine (IUPAC name) (23)+COMPOUND OF FORMULA        I, thiram (804)+COMPOUND OF FORMULA I, trimethacarb        (840)+COMPOUND OF FORMULA I, zinc naphthenate [CCN] and ziram        (856)+COMPOUND OF FORMULA I,    -   a virucide selected from the group of substances consisting of        imanin (alternative name) [CCN] and ribavirin (alternative name)        [CCN]+COMPOUND OF FORMULA I,    -   a wound protectant selected from the group of substances        consisting of mercuric oxide (512)+COMPOUND OF FORMULA I,        octhilinone (590) and thiophanate-methyl (802)+COMPOUND OF        FORMULA I,    -   an insecticide selected from the group consisting of the        compound of the formula A-1

the formula A-2

the formula A-3

the formula A-4

the formula A-5

the formula A-6

the formula A-7

the formula A-8

the formula A-9

the formula A-10

the formula A-11

the formula A-12

the formula A-13

the formula A-14

the formula A-15

the formula A-16

the formula A-17

the formula A-18

the formula A-19

the formula A-20

the formula A-21

the formula A-22

the formula A-23

the formula A-24

the formula A-25

the formula A-26

and the formula A-27

-   -   an insecticide selected from the group consisting of the        compound of the formula A-28

and the formula A-29

and the formula A-30

-   -   an insecticide selected from the group consisting of the        compound of the formula A-31 [BYI2960]

the formula A-32

the formula A-33

-   -   and an insecticide of the formula A-34

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. Thecompounds of the formula A-1 to A-26 are described in WO 03/015518 or inWO 04/067528. The compound of the formula A-27 is described in WO06/022225 and in WO 07/112,844. The above described mixing partners areknown. Where the active ingredients are included in “The PesticideManual” [The Pesticide Manual—A World Compendium; Thirteenth Edition;Editor: C. D. S. TomLin; The British Crop Protection Council], they aredescribed therein under the entry number given in round bracketshereinabove for the particular compound; for example, the compound“abamectin” is described under entry number (1). Where “[CCN]” is addedhereinabove to the particular compound, the compound in question isincluded in the “Compendium of Pesticide Common Names”, which isaccessible on the internet [A. Wood; Compendium of Pesticide CommonNames, Copyright 1995-2004]; for example, the compound “acetoprole” isdescribed under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.htmL.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “development code”is used or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed. “CAS Reg. No” means theChemical Abstracts Registry Number.

The compounds of formula I according to the invention can also be usedin combination with one or more fungicides. In particular, in thefollowing mixtures of the compounds of formula I with fungicides, theterm COMPOUND OF FORMULA I preferably refers to a compound selected fromone of the Tables 1 to 155:

-   COMPOUND OF FORMULA    I+(E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide    (SSF-129), COMPOUND OF FORMULA    I+4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide,    COMPOUND OF FORMULA    I+α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone,    COMPOUND OF FORMULA    I+4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (1    KF-916, cyamidazosulfamid), COMPOUND OF FORMULA    I+3-5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide    (RH-7281, zoxamide), COMPOUND OF FORMULA    I+N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide    (MON65500), COMPOUND OF FORMULA    I+N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide    (AC382042), COMPOUND OF FORMULA    I+N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, COMPOUND OF    FORMULA I+acibenzolar, COMPOUND OF FORMULA I+alanycarb, COMPOUND OF    FORMULA I+aldimorph, COMPOUND OF FORMULA I+ametoctradin, COMPOUND OF    FORMULA I+amisulbrom, COMPOUND OF FORMULA I+anilazine, COMPOUND OF    FORMULA I+azaconazole, COMPOUND OF FORMULA I+azoxystrobin, COMPOUND    OF FORMULA I+benalaxyl, COMPOUND OF FORMULA I+benalaxyl-M, COMPOUND    OF FORMULA I+benomyl, COMPOUND OF FORMULA I+benthiavalicarb,    COMPOUND OF FORMULA I+benzodiflupyr, COMPOUND OF FORMULA    I+benzovindiflupyr, COMPOUND OF FORMULA I+biloxazol, COMPOUND OF    FORMULA I+bitertanol, COMPOUND OF FORMULA I+bixafen, COMPOUND OF    FORMULA I+blasticidin S, COMPOUND OF FORMULA I+boscalid, COMPOUND OF    FORMULA I+bromuconazole, COMPOUND OF FORMULA I+bupirimate, COMPOUND    OF FORMULA I+captafol, COMPOUND OF FORMULA I+captan, COMPOUND OF    FORMULA I+carbendazim, COMPOUND OF FORMULA I+carbendazim    chlorhydrate, COMPOUND OF FORMULA I+carboxin, COMPOUND OF FORMULA    I+carpropamid, carvone, COMPOUND OF FORMULA I+CGA41396, COMPOUND OF    FORMULA I+CGA41397, COMPOUND OF FORMULA I+chinomethionate, COMPOUND    OF FORMULA I+chlazafenone, COMPOUND OF FORMULA I+chlorodincarb,    COMPOUND OF FORMULA I+chlorothalonil, COMPOUND OF FORMULA    I+chlorozolinate, COMPOUND OF FORMULA I+clozylacon, COMPOUND OF    FORMULA I+copper containing compounds such as copper oxychloride,    copper oxyquinolate, copper sulphate, copper tallate and Bordeaux    mixture, COMPOUND OF FORMULA I+coumoxystrobin, COMPOUND OF FORMULA    I+cyazofamid, COMPOUND OF FORMULA I+cyflufenamid, COMPOUND OF    FORMULA I+cymoxanil, COMPOUND OF FORMULA I+cyproconazole, COMPOUND    OF FORMULA I+cyprodinil, COMPOUND OF FORMULA I+debacarb, COMPOUND OF    FORMULA I+di-2-pyridyl disulphide 1,1′-dioxide, COMPOUND OF FORMULA    I+dicloaminstrobin, COMPOUND OF FORMULA I+diclofenoxystrobin,    COMPOUND OF FORMULA I+dichlofluanid, COMPOUND OF FORMULA    I+diclomezine, COMPOUND OF FORMULA I+dicloran, COMPOUND OF FORMULA    I+diethofencarb, COMPOUND OF FORMULA I+difenoconazole, COMPOUND OF    FORMULA I+difenzoquat, COMPOUND OF FORMULA I+diflumetorim, COMPOUND    OF FORMULA I+O,O-di-iso-propyl-5-benzyl thiophosphate, COMPOUND OF    FORMULA I+dimefluazole, COMPOUND OF FORMULA I+dimetconazole,    COMPOUND OF FORMULA I+dimethomorph, COMPOUND OF FORMULA    I+dimethirimol, COMPOUND OF FORMULA I+dimoxystrobin, COMPOUND OF    FORMULA I+diniconazole, COMPOUND OF FORMULA I+dinocap, COMPOUND OF    FORMULA I+dithianon, COMPOUND OF FORMULA I+dodecyl dimethyl ammonium    chloride, COMPOUND OF FORMULA I+dodemorph, COMPOUND OF FORMULA    I+dodine, COMPOUND OF FORMULA I+doguadine, COMPOUND OF FORMULA    I+edifenphos, COMPOUND OF FORMULA I+enoxastrobin, COMPOUND OF    FORMULA I+epoxiconazole, COMPOUND OF FORMULA I+ethirimol, COMPOUND    OF FORMULA    I+ethyl(Z)-N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β-alaninate,    COMPOUND OF FORMULA I+etridiazole, COMPOUND OF FORMULA I+famoxadone,    COMPOUND OF FORMULA I+fenamidone (RPA407213), COMPOUND OF FORMULA    I+fenaminstrobin, COMPOUND OF FORMULA I+fenarimol, COMPOUND OF    FORMULA I+fenbuconazole, COMPOUND OF FORMULA I+fenfuram, COMPOUND OF    FORMULA I+fenhexamid (KBR2738), COMPOUND OF FORMULA I+fenoxanil,    COMPOUND OF FORMULA I+fenoxystrobin, COMPOUND OF FORMULA    I+fenpiclonil, COMPOUND OF FORMULA I+fenpropidin, COMPOUND OF    FORMULA I+fenpropimorph, COMPOUND OF FORMULA I+fenpyrazamine,    COMPOUND OF FORMULA I+fenpyrazamine/ipfenpyrazolone, COMPOUND OF    FORMULA I+fentin acetate, COMPOUND OF FORMULA I+fentin hydroxide,    COMPOUND OF FORMULA I+ferbam, COMPOUND OF FORMULA I+ferimzone,    COMPOUND OF FORMULA I+fluazinam, COMPOUND OF FORMULA I+fludioxonil,    COMPOUND OF FORMULA I+flufenoxystrobin, COMPOUND OF FORMULA    I+flumetover, COMPOUND OF FORMULA I+flumorph, COMPOUND OF FORMULA    I+fluopicolide, COMPOUND OF FORMULA I+fluopyram, COMPOUND OF FORMULA    I+fluoxastrobin, COMPOUND OF FORMULA I+fluoroimide, COMPOUND OF    FORMULA I+fluquinconazole, COMPOUND OF FORMULA I+flusilazole,    COMPOUND OF FORMULA I+flutianil, COMPOUND OF FORMULA I+flutolanil,    COMPOUND OF FORMULA I+flutriafol, COMPOUND OF FORMULA    I+fluxapyroxad, COMPOUND OF FORMULA I+folpet, COMPOUND OF FORMULA    I+fosetyl, COMPOUND OF FORMULA I+fosetyl-aluminium, COMPOUND OF    FORMULA I+fuberidazole, COMPOUND OF FORMULA I+furalaxyl, COMPOUND OF    FORMULA I+furametpyr, COMPOUND OF FORMULA I+guazatine, COMPOUND OF    FORMULA I+hexaconazole, COMPOUND OF FORMULA I+hydroxyisoxazole,    COMPOUND OF FORMULA I+hymexazole, COMPOUND OF FORMULA I+imazalil,    COMPOUND OF FORMULA I+imibenconazole, COMPOUND OF FORMULA    I+iminoctadine, COMPOUND OF FORMULA I+iminoctadine triacetate,    COMPOUND OF FORMULA I+ipconazole, COMPOUND OF FORMULA I+iprobenfos,    COMPOUND OF FORMULA I+iprodione, COMPOUND OF FORMULA I+iprovalicarb    (SZX0722), COMPOUND OF FORMULA I+isopropanyl butyl carbamate,    COMPOUND OF FORMULA I+isoprothiolane, COMPOUND OF FORMULA    I+isopyrazam, COMPOUND OF FORMULA I+isotianil, COMPOUND OF FORMULA    I+kasugamycin, COMPOUND OF FORMULA I+kresoxim-methyl, COMPOUND OF    FORMULA I+LY186054, COMPOUND OF FORMULA I+LY211795, COMPOUND OF    FORMULA I+LY248908, COMPOUND OF FORMULA I+mancozeb, COMPOUND OF    FORMULA I+mandipropamid, COMPOUND OF FORMULA I+maneb, COMPOUND OF    FORMULA I+mefenoxam, COMPOUND OF FORMULA I+mepanipyrim, COMPOUND OF    FORMULA I+mepronil, COMPOUND OF FORMULA I+meptyldinocap, COMPOUND OF    FORMULA I+metalaxyl, COMPOUND OF FORMULA I+metconazole, COMPOUND OF    FORMULA I+metiram, COMPOUND OF FORMULA I+metiram-zinc, COMPOUND OF    FORMULA I+metominostrobin, COMPOUND OF FORMULA I+metrafenone,    COMPOUND OF FORMULA I+myclobutanil, COMPOUND OF FORMULA I+neoasozin,    COMPOUND OF FORMULA I+nickel dimethyldithiocarbamate, COMPOUND OF    FORMULA I+nicobifen, COMPOUND OF FORMULA I+nitrothal-isopropyl,    COMPOUND OF FORMULA I+nuarimol, COMPOUND OF FORMULA I+ofurace,    COMPOUND OF FORMULA I+organomercury compounds, COMPOUND OF FORMULA    I+orysastrobin, COMPOUND OF FORMULA I+oxadixyl, COMPOUND OF FORMULA    I+oxasulfuron, COMPOUND OF FORMULA I+oxolinic acid, COMPOUND OF    FORMULA I+oxpoconazole, COMPOUND OF FORMULA I+oxycarboxin, COMPOUND    OF FORMULA I+pefurazoate, COMPOUND OF FORMULA I+penconazole,    COMPOUND OF FORMULA I+pencycuron, COMPOUND OF FORMULA I+penflufen,    COMPOUND OF FORMULA I+penthiopyrad, COMPOUND OF FORMULA I+phenazin    oxide, COMPOUND OF FORMULA I+phosetyl-Al, COMPOUND OF FORMULA    I+phosphorus acids, COMPOUND OF FORMULA I+phthalide, COMPOUND OF    FORMULA I+picoxystrobin (ZA1963), COMPOUND OF FORMULA I+polyoxin D,    COMPOUND OF FORMULA I+polyram, COMPOUND OF FORMULA I+probenazole,    COMPOUND OF FORMULA I+prochloraz, COMPOUND OF FORMULA I+procymidone,    COMPOUND OF FORMULA I+propamocarb, COMPOUND OF FORMULA    I+propiconazole, COMPOUND OF FORMULA I+propineb, COMPOUND OF FORMULA    I+propionic acid, COMPOUND OF FORMULA I+proquinazid, COMPOUND OF    FORMULA I+prothioconazole, COMPOUND OF FORMULA I+pyraclostrobin,    COMPOUND OF FORMULA I+pyraoxystrobin, COMPOUND OF FORMULA    I+pyrazophos, COMPOUND OF FORMULA I+pyribencarb, COMPOUND OF FORMULA    I+pyrifenox, COMPOUND OF FORMULA I+pyrimethanil, COMPOUND OF FORMULA    I+pyrisoxazole, COMPOUND OF FORMULA I+pyroquilon, COMPOUND OF    FORMULA I+pyroxyfur, COMPOUND OF FORMULA I+pyrroInitrin, COMPOUND OF    FORMULA I+quaternary ammonium compounds, COMPOUND OF FORMULA    I+quinomethionate, COMPOUND OF FORMULA I+quinoxyfen, COMPOUND OF    FORMULA I+quintozene, COMPOUND OF FORMULA I+sedaxane, COMPOUND OF    FORMULA I+sipconazole (F-155), COMPOUND OF FORMULA I+sodium    pentachlorophenate, COMPOUND OF FORMULA I+spiroxamine, COMPOUND OF    FORMULA I+streptomycin, COMPOUND OF FORMULA I+sulphur, COMPOUND OF    FORMULA I+tebuconazole, COMPOUND OF FORMULA I+tecloftalam, COMPOUND    OF FORMULA I+tecnazene, COMPOUND OF FORMULA I+terbufloquin, COMPOUND    OF FORMULA I+tetraconazole, COMPOUND OF FORMULA I+thiabendazole,    COMPOUND OF FORMULA I+thifluzamid, COMPOUND OF FORMULA    I+2-(thiocyanomethylthio)benzothiazole, COMPOUND OF FORMULA    I+thiophanate-methyl, COMPOUND OF FORMULA I+thiram, COMPOUND OF    FORMULA I+tiadinil, COMPOUND OF FORMULA I+timibenconazole, COMPOUND    OF FORMULA I+tolclofos-methyl, COMPOUND OF FORMULA I+tolylfluanid,    COMPOUND OF FORMULA I+triadimefon, COMPOUND OF FORMULA    I+triadimenol, COMPOUND OF FORMULA I+triazbutil, COMPOUND OF FORMULA    I+triazoxide, COMPOUND OF FORMULA I+triclopyricarb, COMPOUND OF    FORMULA I+tricyclazole, COMPOUND OF FORMULA I+tridemorph, COMPOUND    OF FORMULA I+trifloxystrobin, COMPOUND OF FORMULA I+triforine,    COMPOUND OF FORMULA I+triflumizole, COMPOUND OF FORMULA    I+triticonazole, COMPOUND OF FORMULA I+validamycin A, COMPOUND OF    FORMULA I+valiphenal, COMPOUND OF FORMULA I+vapam, COMPOUND OF    FORMULA I+vinclozolin, COMPOUND OF FORMULA I+zineb and COMPOUND OF    FORMULA I+ziram.

The compounds of formula I may be mixed with soil, peat or other rootingmedia for the protection of plants against seed-borne, soil-borne orfoliar fungal diseases.

The compounds of formula I according to the invention can also be usedin combination with one or more other synergists. In particular, thefollowing mixtures of the COMPOUND OF FORMULA I, where this termpreferably refers to a compound selected from one of the Tables 1 to155, are important:

-   COMPOUND OF FORMULA I+piperonyl butoxide, COMPOUND OF FORMULA    I+sesamex, COMPOUND OF FORMULA I+safroxan and COMPOUND OF FORMULA    I+dodecyl imidazole.

The compounds of formula I according to the invention can also be usedin combination with one or more other herbicides. In particular, thefollowing mixtures of the COMPOUND OF FORMULA I, where this termpreferably refers to a compound selected from one of the Tables 1 to155, are important:

-   COMPOUND OF FORMULA I+acetochlor, COMPOUND OF FORMULA I+acifluorfen,    COMPOUND OF FORMULA I+acifluorfen-sodium, COMPOUND OF FORMULA    I+aclonifen, COMPOUND OF FORMULA I+acrolein, COMPOUND OF FORMULA    I+alachlor, COMPOUND OF FORMULA I+alloxydim, COMPOUND OF FORMULA    I+allyl alcohol, COMPOUND OF FORMULA I+ametryn, COMPOUND OF FORMULA    I+amicarbazone, COMPOUND OF FORMULA I+amidosulfuron, COMPOUND OF    FORMULA I+aminocyclopyrachlor, COMPOUND OF FORMULA I+aminopyralid,    COMPOUND OF FORMULA I+amitrole, COMPOUND OF FORMULA I+ammonium    sulfamate, COMPOUND OF FORMULA I+anilofos, COMPOUND OF FORMULA    I+asulam, COMPOUND OF FORMULA I+atraton, COMPOUND OF FORMULA    I+atrazine, COMPOUND OF FORMULA I+azimsulfuron, COMPOUND OF FORMULA    I+BCPC, COMPOUND OF FORMULA I+beflubutamid, COMPOUND OF FORMULA    I+benazolin, COMPOUND OF FORMULA I+bencarbazone, COMPOUND OF FORMULA    I+benfluralin, COMPOUND OF FORMULA I+benfuresate, COMPOUND OF    FORMULA I+bensulfuron, COMPOUND OF FORMULA I+bensulfuron-methyl,    COMPOUND OF FORMULA I+bensulide, COMPOUND OF FORMULA I+bentazone,    COMPOUND OF FORMULA I+benzfendizone, COMPOUND OF FORMULA    I+benzobicyclon, COMPOUND OF FORMULA I+benzofenap, COMPOUND OF THE    FORMULA I+bicyclopyrone, COMPOUND OF FORMULA I+bifenox, COMPOUND OF    FORMULA I+bilanafos, COMPOUND OF FORMULA I+bispyribac, COMPOUND OF    FORMULA I+bispyribac-sodium, COMPOUND OF FORMULA I+borax, COMPOUND    OF FORMULA I+bromacil, COMPOUND OF FORMULA I+bromobutide, COMPOUND    OF FORMULA I+bromoxynil, COMPOUND OF FORMULA I+butachlor, COMPOUND    OF FORMULA I+butafenacil, COMPOUND OF FORMULA I+butamifos, COMPOUND    OF FORMULA I+butralin, COMPOUND OF FORMULA I+butroxydim, COMPOUND OF    FORMULA I+butylate, COMPOUND OF FORMULA I+cacodylic acid, COMPOUND    OF FORMULA I+calcium chlorate, COMPOUND OF FORMULA I+cafenstrole,    COMPOUND OF FORMULA I+carbetamide, COMPOUND OF FORMULA    I+carfentrazone, COMPOUND OF FORMULA I+carfentrazone-ethyl, COMPOUND    OF FORMULA I+CDEA, COMPOUND OF FORMULA I+CEPC, COMPOUND OF FORMULA    I+chlorflurenol, COMPOUND OF FORMULA I+chlorflurenol-methyl,    COMPOUND OF FORMULA I+chloridazon, COMPOUND OF FORMULA    I+chlorimuron, COMPOUND OF FORMULA I+chlorimuron-ethyl, COMPOUND OF    FORMULA I+chloroacetic acid, COMPOUND OF FORMULA I+chlorotoluron,    COMPOUND OF FORMULA I+chlorpropham, COMPOUND OF FORMULA    I+chlorsulfuron, COMPOUND OF FORMULA I+chlorthal, COMPOUND OF    FORMULA I+chlorthal-dimethyl, COMPOUND OF FORMULA I+cinidon-ethyl,    COMPOUND OF FORMULA I+cinmethylin, COMPOUND OF FORMULA    I+cinosulfuron, COMPOUND OF FORMULA I+cisanilide, COMPOUND OF    FORMULA I+clethodim, COMPOUND OF FORMULA I+clodinafop, COMPOUND OF    FORMULA I+clodinafop-propargyl, COMPOUND OF FORMULA I+clomazone,    COMPOUND OF FORMULA I+clomeprop, COMPOUND OF FORMULA I+clopyralid,    COMPOUND OF FORMULA I+cloransulam, COMPOUND OF FORMULA    I+cloransulam-methyl, COMPOUND OF FORMULA I+CMA, COMPOUND OF FORMULA    I+4-CPB, COMPOUND OF FORMULA I+CPMF, COMPOUND OF FORMULA I+4-CPP,    COMPOUND OF FORMULA I+CPPC, COMPOUND OF FORMULA I+cresol, COMPOUND    OF FORMULA I+cumyluron, COMPOUND OF FORMULA I+cyanamide, COMPOUND OF    FORMULA I+cyanazine, COMPOUND OF FORMULA I+cycloate, COMPOUND OF    FORMULA I+cyclosulfamuron, COMPOUND OF FORMULA I+cycloxydim,    COMPOUND OF FORMULA I+cyhalofop, COMPOUND OF FORMULA    I+cyhalofop-butyl, COMPOUND OF FORMULA I+2,4-D, COMPOUND OF FORMULA    I+3,4-DA, COMPOUND OF FORMULA I+daimuron, COMPOUND OF FORMULA    I+dalapon, COMPOUND OF FORMULA I+dazomet, COMPOUND OF FORMULA    I+2,4-DB, COMPOUND OF FORMULA I+3,4-DB, COMPOUND OF FORMULA    I+2,4-DEB, COMPOUND OF FORMULA I+desmedipham, COMPOUND OF FORMULA    I+dicamba, COMPOUND OF FORMULA I+dichlobenil, COMPOUND OF FORMULA    I+ortho-dichlorobenzene, COMPOUND OF FORMULA I+para-dichlorobenzene,    COMPOUND OF FORMULA I+dichlorprop, COMPOUND OF FORMULA    I+dichlorprop-P, COMPOUND OF FORMULA I+diclofop, COMPOUND OF FORMULA    I+diclofop-methyl, COMPOUND OF FORMULA I+diclosulam, COMPOUND OF    FORMULA I+difenzoquat, COMPOUND OF FORMULA I+difenzoquat    metilsulfate, COMPOUND OF FORMULA I+diflufenican, COMPOUND OF    FORMULA I+diflufenzopyr, COMPOUND OF FORMULA I+dimefuron, COMPOUND    OF FORMULA I+dimepiperate, COMPOUND OF FORMULA I+dimethachlor,    COMPOUND OF FORMULA I+dimethametryn, COMPOUND OF FORMULA    I+dimethenamid, COMPOUND OF FORMULA I+dimethenamid-P, COMPOUND OF    FORMULA I+dimethipin, COMPOUND OF FORMULA I+dimethylarsinic acid,    COMPOUND OF FORMULA I+dinitramine, COMPOUND OF FORMULA I+dinoterb,    COMPOUND OF FORMULA I+diphenamid, COMPOUND OF FORMULA I+diquat,    COMPOUND OF FORMULA I+diquat dibromide, COMPOUND OF FORMULA    I+dithiopyr, COMPOUND OF FORMULA I+diuron, COMPOUND OF FORMULA    I+DNOC, COMPOUND OF FORMULA I+3,4-DP, COMPOUND OF FORMULA I+DSMA,    COMPOUND OF FORMULA I+EBEP, COMPOUND OF FORMULA I+endothal, COMPOUND    OF FORMULA I+EPTC, COMPOUND OF FORMULA I+esprocarb, COMPOUND OF    FORMULA I+ethalfluralin, COMPOUND OF FORMULA I+ethametsulfuron,    COMPOUND OF FORMULA I+ethametsulfuron-methyl, COMPOUND OF FORMULA    I+ethofumesate, COMPOUND OF FORMULA I+ethoxyfen, COMPOUND OF FORMULA    I+ethoxysulfuron, COMPOUND OF FORMULA I+etobenzanid, COMPOUND OF    FORMULA I+fenoxaprop-P, COMPOUND OF FORMULA I+fenoxaprop-P-ethyl,    COMPOUND OF FORMULA I+fentrazamide, COMPOUND OF FORMULA I+ferrous    sulfate, COMPOUND OF FORMULA I+flamprop-M, COMPOUND OF FORMULA    I+flazasulfuron, COMPOUND OF FORMULA I+florasulam, COMPOUND OF    FORMULA I+fluazifop, COMPOUND OF FORMULA I+fluazifop-butyl, COMPOUND    OF FORMULA I+fluazifop-P, COMPOUND OF FORMULA I+fluazifop-P-butyl,    COMPOUND OF FORMULA I+flucarbazone, COMPOUND OF FORMULA    I+flucarbazone-sodium, COMPOUND OF FORMULA I+flucetosulfuron,    COMPOUND OF FORMULA I+fluchloralin, COMPOUND OF FORMULA    I+flufenacet, COMPOUND OF FORMULA I+flufenpyr, COMPOUND OF FORMULA    I+flufenpyr-ethyl, COMPOUND OF FORMULA I+flumetsulam, COMPOUND OF    FORMULA I+flumiclorac, COMPOUND OF FORMULA I+flumiclorac-pentyl,    COMPOUND OF FORMULA I+flumioxazin, COMPOUND OF FORMULA    I+fluometuron, COMPOUND OF FORMULA I+fluoroglycofen, COMPOUND OF    FORMULA I+fluoroglycofen-ethyl, COMPOUND OF FORMULA I+flupropanate,    COMPOUND OF FORMULA I+flupyrsulfuron, COMPOUND OF FORMULA    I+flupyrsulfuron-methyl-sodium, COMPOUND OF FORMULA I+flurenol,    COMPOUND OF FORMULA I+fluridone, COMPOUND OF FORMULA    I+fluorochloridone, COMPOUND OF FORMULA I+fluoroxypyr, COMPOUND OF    FORMULA I+flurtamone, COMPOUND OF FORMULA I+fluthiacet, COMPOUND OF    FORMULA I+fluthiacet-methyl, COMPOUND OF FORMULA I+fomesafen,    COMPOUND OF FORMULA I+foramsulfuron, COMPOUND OF FORMULA I+fosamine,    COMPOUND OF FORMULA I+glufosinate, COMPOUND OF FORMULA    I+glufosinate-ammonium, COMPOUND OF FORMULA I+glufosinate-P,    COMPOUND OF FORMULA I+glyphosate, COMPOUND OF FORMULA    I+glyphosate-trimesium, COMPOUND OF FORMULA I+halosulfuron, COMPOUND    OF FORMULA I+halosulfuron-methyl, COMPOUND OF FORMULA I+haloxyfop,    COMPOUND OF FORMULA I+haloxyfop-P, COMPOUND OF FORMULA I+HC-252,    COMPOUND OF FORMULA I+hexazinone, COMPOUND OF FORMULA    I+imazamethabenz, COMPOUND OF FORMULA I+imazamethabenz-methyl,    COMPOUND OF FORMULA I+imazamox, COMPOUND OF FORMULA I+imazapic,    COMPOUND OF FORMULA I+imazapyr, COMPOUND OF FORMULA I+imazaquin,    COMPOUND OF FORMULA I+imazethapyr, COMPOUND OF FORMULA    I+imazosulfuron, COMPOUND OF FORMULA I+indanofan, COMPOUND OF    FORMULA I+indaziflam, COMPOUND OF FORMULA I+iodomethane, COMPOUND OF    FORMULA I+iodosulfuron, COMPOUND OF FORMULA    I+iodosulfuron-methyl-sodium, COMPOUND OF FORMULA I+iofensulfuron,    COMPOUND OF FORMULA I+ioxynil, COMPOUND OF FORMULA I+ipfencarbazone,    COMPOUND OF FORMULA I+isoproturon, COMPOUND OF FORMULA I+isouron,    COMPOUND OF FORMULA I+isoxaben, COMPOUND OF FORMULA    I+isoxachlortole, COMPOUND OF FORMULA I+isoxaflutole, COMPOUND OF    FORMULA I+karbutilate, COMPOUND OF FORMULA I+lactofen, COMPOUND OF    FORMULA I+lenacil, COMPOUND OF FORMULA I+linuron, COMPOUND OF    FORMULA I+MAA, COMPOUND OF FORMULA I+MAMA, COMPOUND OF FORMULA    I+MCPA, COMPOUND OF FORMULA I+MCPA-thioethyl, COMPOUND OF FORMULA    I+MCPB, COMPOUND OF FORMULA I+mecoprop, COMPOUND OF FORMULA    I+mecoprop-P, COMPOUND OF FORMULA I+mefenacet, COMPOUND OF FORMULA    I+mefluidide, COMPOUND OF FORMULA I+mesosulfuron, COMPOUND OF    FORMULA I+mesosulfuron-methyl, COMPOUND OF FORMULA I+mesotrione,    COMPOUND OF FORMULA I+metam, COMPOUND OF FORMULA I+metamifop,    COMPOUND OF FORMULA I+metamitron, COMPOUND OF FORMULA I+metazachlor,    COMPOUND OF FORMULA I+methabenzthiazuron, COMPOUND OF FORMULA    I+methylarsonic acid, COMPOUND OF FORMULA I+methyldymron, COMPOUND    OF FORMULA I+methyl isothiocyanate, COMPOUND OF FORMULA    I+metiozolin, COMPOUND OF FORMULA I+metobenzuron, COMPOUND OF    FORMULA I+metolachlor, COMPOUND OF FORMULA I+S-metolachlor, COMPOUND    OF FORMULA I+metosulam, COMPOUND OF FORMULA I+metoxuron, COMPOUND OF    FORMULA I+metribuzin, COMPOUND OF FORMULA I+metsulfuron, COMPOUND OF    FORMULA I+metsulfuron-methyl, COMPOUND OF FORMULA I+MK-616, COMPOUND    OF FORMULA I+molinate, COMPOUND OF FORMULA I+monolinuron, COMPOUND    OF FORMULA I+MSMA, COMPOUND OF FORMULA I+naproanilide, COMPOUND OF    FORMULA I+napropamide, COMPOUND OF FORMULA I+naptalam, COMPOUND OF    FORMULA I+neburon, COMPOUND OF FORMULA I+nicosulfuron, COMPOUND OF    FORMULA I+nonanoic acid, COMPOUND OF FORMULA I+norflurazon, COMPOUND    OF FORMULA I+oleic acid (fatty acids), COMPOUND OF FORMULA    I+orbencarb, COMPOUND OF FORMULA I+orthosulfamuron, COMPOUND OF    FORMULA I+oryzalin, COMPOUND OF FORMULA I+oxadiargyl, COMPOUND OF    FORMULA I+oxadiazon, COMPOUND OF FORMULA I+oxasulfuron, COMPOUND OF    FORMULA I+oxaziclomefone, COMPOUND OF FORMULA I+oxyfluorfen,    COMPOUND OF FORMULA I+paraquat, COMPOUND OF FORMULA I+paraquat    dichloride, COMPOUND OF FORMULA I+pebulate, COMPOUND OF FORMULA    I+pendimethalin, COMPOUND OF FORMULA I+penoxsulam, COMPOUND OF    FORMULA I+pentachlorophenol, COMPOUND OF FORMULA I+pentanochlor,    COMPOUND OF FORMULA I+pentoxazone, COMPOUND OF FORMULA I+pethoxamid,    COMPOUND OF FORMULA I+petrolium oils, COMPOUND OF FORMULA    I+phenmedipham, COMPOUND OF FORMULA I+phenmedipham-ethyl, COMPOUND    OF FORMULA I+picloram, COMPOUND OF FORMULA I+picolinafen, COMPOUND    OF FORMULA I+pinoxaden, COMPOUND OF FORMULA I+piperophos, COMPOUND    OF FORMULA I+potassium arsenite, COMPOUND OF FORMULA I+potassium    azide, COMPOUND OF FORMULA I+pretilachlor, COMPOUND OF FORMULA    I+primisulfuron, COMPOUND OF FORMULA I+primisulfuron-methyl,    COMPOUND OF FORMULA I+prodiamine, COMPOUND OF FORMULA I+profluazol,    COMPOUND OF FORMULA I+profoxydim, COMPOUND OF FORMULA I+prometon,    COMPOUND OF FORMULA I+prometryn, COMPOUND OF FORMULA I+propachlor,    COMPOUND OF FORMULA I+propanil, COMPOUND OF FORMULA I+propaquizafop,    COMPOUND OF FORMULA I+propazine, COMPOUND OF FORMULA I+propham,    COMPOUND OF FORMULA I+propisochlor, COMPOUND OF FORMULA    I+propoxycarbazone, COMPOUND OF FORMULA I+propoxycarbazone-sodium,    COMPOUND OF FORMULA I+propyrisulfuron, COMPOUND OF FORMULA    I+propyzamide, COMPOUND OF FORMULA I+prosulfocarb, COMPOUND OF    FORMULA I+prosulfuron, COMPOUND OF FORMULA I+pyraclonil, COMPOUND OF    FORMULA I+pyraflufen, COMPOUND OF FORMULA I+pyraflufen-ethyl,    COMPOUND OF FORMULA I+pyrasulfutole, COMPOUND OF FORMULA    I+pyrazolynate, COMPOUND OF FORMULA I+pyrazosulfuron, COMPOUND OF    FORMULA I+pyrazosulfuron-ethyl, COMPOUND OF FORMULA I+pyrazoxyfen,    COMPOUND OF FORMULA I+pyribenzoxim, COMPOUND OF FORMULA    I+pyributicarb, COMPOUND OF FORMULA I+pyridafol, COMPOUND OF FORMULA    I+pyridate, COMPOUND OF FORMULA I+pyriftalid, COMPOUND OF FORMULA    I+pyriminobac, COMPOUND OF FORMULA I+pyriminobac-methyl, COMPOUND OF    FORMULA I+pyrimisulfan, COMPOUND OF FORMULA I+pyrithiobac, COMPOUND    OF FORMULA I+pyrithiobac-sodium, COMPOUND OF FORMULA I+pyroxsulam,    COMPOUND OF FORMULA I+pyroxasulfone, COMPOUND OF FORMULA    I+quinclorac, COMPOUND OF FORMULA I+quinmerac, COMPOUND OF FORMULA    I+quinoclamine, COMPOUND OF FORMULA I+quizalofop, COMPOUND OF    FORMULA I+quizalofop-P, COMPOUND OF FORMULA I+rimsulfuron, COMPOUND    OF FORMULA I+saflufenacil, COMPOUND OF FORMULA I+sethoxydim,    COMPOUND OF FORMULA I+siduron, COMPOUND OF FORMULA I+simazine,    COMPOUND OF FORMULA I+simetryn, COMPOUND OF FORMULA I+SMA, COMPOUND    OF FORMULA I+sodium arsenite, COMPOUND OF FORMULA I+sodium azide,    COMPOUND OF FORMULA I+sodium chlorate, COMPOUND OF FORMULA    I+sulcotrione, COMPOUND OF FORMULA I+sulfentrazone, COMPOUND OF    FORMULA I+sulfometuron, COMPOUND OF FORMULA I+sulfometuron-methyl,    COMPOUND OF FORMULA I+sulfosate, COMPOUND OF FORMULA    I+sulfosulfuron, COMPOUND OF FORMULA I+sulfuric acid, COMPOUND OF    FORMULA I+tar oils, COMPOUND OF FORMULA I+2,3,6-TBA, COMPOUND OF    FORMULA I+TCA, COMPOUND OF FORMULA I+TCA-sodium, COMPOUND OF FORMULA    I+tebuthiuron, COMPOUND OF FORMULA I+tefuryltrione, COMPOUND OF    FORMULA I+tembotrione, COMPOUND OF FORMULA I+tepraloxydim, COMPOUND    OF FORMULA I+terbacil, COMPOUND OF FORMULA I+terbumeton, COMPOUND OF    FORMULA I+terbuthylazine, COMPOUND OF FORMULA I+terbutryn, COMPOUND    OF FORMULA I+thenylchlor, COMPOUND OF FORMULA I+thiazopyr, COMPOUND    OF FORMULA I+thiencarbazone, COMPOUND OF FORMULA    I+thiencarbazone-methyl, COMPOUND OF FORMULA I+thifensulfuron,    COMPOUND OF FORMULA I+thifensulfuron-methyl, COMPOUND OF FORMULA    I+thiobencarb, COMPOUND OF FORMULA I+tiocarbazil, COMPOUND OF    FORMULA I+topramezone, COMPOUND OF FORMULA I+tralkoxydim, COMPOUND    OF FORMULA I+triafamone, COMPOUND OF FORMULA I+tri-allate, COMPOUND    OF FORMULA I+triasulfuron, COMPOUND OF FORMULA I+triaziflam,    COMPOUND OF FORMULA I+tribenuron, COMPOUND OF FORMULA    I+tribenuron-methyl, COMPOUND OF FORMULA I+tricamba, COMPOUND OF    FORMULA I+triclopyr, COMPOUND OF FORMULA I+trietazine, COMPOUND OF    FORMULA I+trifloxysulfuron, COMPOUND OF FORMULA    I+trifloxysulfuron-sodium, COMPOUND OF FORMULA I+trifluralin,    COMPOUND OF FORMULA I+triflusulfuron, COMPOUND OF FORMULA    I+triflusulfuron-methyl, COMPOUND OF FORMULA I+trihydroxytriazine,    COMPOUND OF FORMULA I+tritosulfuron, COMPOUND OF FORMULA    I+[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic    acid ethyl ester (CAS RN 353292-31-6), COMPOUND OF FORMULA    I+4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo)-1H-1,2,4-triazol-1-ylcarbonylsulfamoyl]-5-methylthiophene-3-carboxylic    acid (BAY636), COMPOUND OF FORMULA I+BAY747 (CAS RN 335104-84-2),    COMPOUND OF FORMULA I+topramezone (CAS RN 210631-68-8), COMPOUND OF    FORMULA    I+4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one    (CAS RN 352010-68-5), COMPOUND OF FORMULA    I+4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one    and COMPOUND OF FORMULA I+ZJ0273.

The compounds of formula (I) according to the invention can also be usedin combination with safeners. Preferably, in these mixtures, thecompound of the formula (I) is one of those compounds listed in Tables 1to 155 above. The following mixtures with safeners, especially, comeinto consideration:

-   compound of formula (I)+cloquintocet-mexyl, compound of formula    (I)+cloquintocet acid and salts thereof, compound of formula    (I)+cyprosulfamide, compound of formula (I)+fenchlorazole-ethyl,    compound of formula (I)+fenchlorazole acid and salts thereof,    compound of formula (I)+mefenpyr-diethyl, compound of formula    (I)+mefenpyr diacid, compound of formula (I)+isoxadifen-ethyl,    compound of formula (I)+isoxadifen acid, compound of formula    (I)+furilazole, compound of formula (I)+furilazole R isomer,    compound of formula (I)+benoxacor, compound of formula    (I)+dichlormid, compound of formula (I)+AD-67, compound of formula    (I)+oxabetrinil, compound of formula (I)+cyometrinil, compound of    formula (I)+cyometrinil Z-isomer, compound of formula (I)+fenclorim,    compound of formula (I)+cyprosulfamide, compound of formula    (I)+naphthalic anhydride, compound of formula (I)+flurazole,    compound of formula    (I)+N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide,    compound of formula (I)+CL 304,415, compound of formula    (I)+dicyclonon, compound of formula (I)+fluxofenim, compound of    formula (I)+DKA-24, compound of formula (I)+R-29148 and compound of    formula (I)+PPG-1292. A safening effect can also be observed for the    mixtures compound of the formula (I)+dymron, compound of the formula    (I)+MCPA, compound of the formula (I)+mecopropand compound of the    formula (I)+mecoprop-P.

The mixing partners of the compound of formula I may also be in the formof esters or salts, as mentioned e.g. in The Pesticide Manual, 12thEdition (BCPC), 2000.

In the above-mentioned mixtures of compounds of formula I, in particulara compound selected from said Tables 1 to 155, with other insecticides,fungicides, herbicides, safeners, adjuvants and the like, the mixingratios can vary over a large range and are, preferably

-   100:1 to 1:6000, especially 50:1 to 1:50, more especially 20:1 to    1:20, even more especially 10:1 to 1:10. Those mixing ratios are    understood to include, on the one hand, ratios by weight and also,    on other hand, molar ratios.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of formula I with the mixing partner).

Some mixtures may comprise active ingredients which have significantlydifferent physical, chemical or biological properties such that they donot easily lend themselves to the same conventional formulation type. Inthese circumstances other formulation types may be prepared. Forexample, where one active ingredient is a water insoluble solid and theother a water insoluble liquid, it may nevertheless be possible todisperse each active ingredient in the same continuous aqueous phase bydispersing the solid active ingredient as a suspension (using apreparation analogous to that of an SC) but dispersing the liquid activeingredient as an emulsion (using a preparation analogous to that of anEW). The resultant composition is a suspoemulsion (SE) formulation.

The mixtures comprising a compound of formula I selected from Tables 1to 155 and one or more active ingredients as described above can beapplied, for example, in a single “ready-mix” form, in a combined spraymixture composed from separate formulations of the single activeingredient components, such as a “tank-mix”, and in a combined use ofthe single active ingredients when applied in a sequential manner, i.e.one after the other with a reasonably short period, such as a few hoursor days. The order of applying the compounds of formula I selected fromTables 1 to 155 and the active ingredients as described above is notessential for working the present invention.

The invention is illustrated by the following preparation examples. TheH-NMR data of certain compounds of this invention show line broadeningat room temperature, suggesting the existence of plural conformationalisomers due to, for example keto-enol tautomerism, hindered rotation,ring inversion in the piperidine moitey or nitrogen inversion at thepiperidine N—OR center. Broad signals have been labeled with ‘br’accordingly.

Example 1 Preparation of4-Hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P2.2)

[Two-Steps (Amide N-Alkylation and Cyclisation), One-Pot Procedure]

To a solution of1-methoxy-4-[2-(2,4,6-trimethyl-phenyl)-acetylamino]-piperidine-4-carboxylicacid methyl ester [prepared according to WO09/049851] (850 mg, 2.44mmol) in dimethylformamide (20 ml) at 0° C. was added sodium hydride(122 mg, 55% w/w dispersion in mineral oil, 2.81 mmol) in two portions.The reaction mixture was stirred at 0° C. for one hour, treated withmethyl iodide (0.175 ml, 398 mg, 2.81 mmol) dropwise, and furtherstirred at 0° C. for one hour and at room temperature for 3 hours. Tothe mixture recooled at 0° C. was added sodium methoxide (198 mg, 3.66mmol) in one portion, and stirring continued at room temperature for 2hours, at 40° C. for 30 minutes and after further addition of sodiummethoxide (˜20 mg) at 50° C. for 45 minutes. The reaction mixture waspoured on iced aqueous ammonium chloride, acidified to pH 5-6 with anaqueous HCl solution and thoroughly extracted with ethyl acetate. Thecombined organic layers were washed with brine, dried over sodiumsulfate and concentrated. The crude oily product was purified bychromatography on silica gel (ethyl acetate), and further trituratedwith cold diethyl ether, filtered and dried. Yield: 338 mg of4-hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(title compound P2.2) as a solid, mp 241-243° C.

¹H-NMR (CD₃OD): 1.44 (br m, 1H), 1.72 (br m, 1H), 2.10 (s, 6H), 2.25 (s,3H), 2.33 (br m, 1H), 2.48 (br m, 1H), 2.89 (br signal, 3H), 3.20 (br m,1H), 3.27-3.43 (br signals, total 3H), 3.54 (s, 3H), 6.89 (s, 2H).

LC/MS (ES+): 331 (M+H)⁺, LC/MS (ES−): 329 (M−H)⁻

Example 2 Preparation of4-Hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P2.2) Step 1: Preparation of4-benzyloxy-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P3.4)

To a suspension of4-hydroxy-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one[prepared according to WO09/049851] (67.0 g, 211.7 mmol) in acetone (900ml) was added potassium carbonate (35.1 g, 254.1 mmol), followed bybenzyl bromide (35.3 ml, 50.7 g, 296.4 mmol) dropewise. The suspensionwas stirred at reflux for one hour, then poured on ice water and ethylacetate. The resulting precipitate was filtered off, dissolved inmethylene chloride, dried over sodium sulfate, concentrated and driedover phosphorus pentoxide under vacuum at 50° C. overnight to afford afirst crop of product as a white solid (55.8 g). The layers of themother liquor were separated, the aqueous phase extracted with ethylacetate, the combined organic phases washed with brine, dried oversodium sulfate and concentrated. The residue was suspended in diethylether, filtered and dried to further deliver 22.6 g of product. Yield:78.4 g of4-benzyloxy-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P3.4) as a solid, mp 184-186° C.

¹H-NMR (CDCl₃): 1.66 (m, 2H), 2.11 (s, 6H), 2.28 (s, 3H), 2.33 (m, 2H),2.47 (m, 2H), 3.45 (m, 2H), 3.55 (s, 3H), 4.68 (s, 2H), 6.13 (br s, 1H),6.87 (s, 2H), 7.04 (m, 2H), 7.28 (m, 3H).

LC/MS (ES+): 407 (M+H)⁺

Step 2: Preparation of4-benzyloxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P3.5)

To a solution of4-benzyloxy-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(40.0 g, 98.4 mmol) in tetrahydrofuran (500 ml) at 0° C. was added a 1.0M solution of lithium bis(trimethylsilyl)amide in tetrahydrofuran (108.3ml, 108.3 mmol) dropwise over one hour. The mixture was stirred at 0° C.for 30 minutes and at room temperature for 30 minutes, then treated withmethyl iodide (6.75 ml, 15.4 g, 108.2 mmol) dropwise at 0° C. over 10minutes. Stirring was continued at room temperature overnight and thereaction mixture was quenched with cold saturated aqueous ammoniumchloride. The layers were separated, the aqueous phase extracted twicewith ethyl acetate, the combined organic phases washed with brine, driedover sodium sulfate and concentrated. The residue was suspended indiethyl ether, stirred for 30 minutes, filtered and dried. Yield: 28.6 gof4-benzyloxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P3.5) as a solid, mp 139-141° C.

¹H-NMR (CDCl₃): 1.52 (br m, 1H), 1.74 (br m, 1H), 2.11 (br s, 6H), 2.28(s, 3H), 2.34 (br m, 2H), 2.92 (br signal, 3H), 3.12 (br m, 1H), 3.30(m, 3H), 3.52 (s, 3H), 4.67 (br signal, 2H), 6.85 (s, 2H), 7.04 (m, 2H),7.28 (m, 3H).

LC/MS (ES+): 421 (M+H)⁺

Step 3: Preparation of4-hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(title compound P2.2)

To a solution of4-benzyloxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(22.6 g, 53.7 mmol) in methanol (226 ml) and water (22.6 ml) in a Parrshaker type hydrogenator was added 5% Pd/C (22.6 g). After hydrogenationunder 4 bars H₂ at 36° C. for 22 hours, the reaction mixture wasfiltered and concentrated. The residue was diluted with ethyl acetateand extracted with saturated aqueous sodium carbonate under ice cooling.The organic layer was discarded, the aqueous alkaline phase acidifiedwith cooling to pH 5-6 with an aqueous HCl solution and thoroughlyextracted with ethyl acetate. The combined organic layers were washedwith brine, dried over sodium sulfate and concentrated. Yield: 13.0 g of4-hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(title compound P2.2) as a solid, mp 239-241° C.

The spectral data were identical to those described above underpreparation example 1.

Example 3 Preparation of1-Cyclopropylmethyl-4-hydroxy-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P2.8) Step 1: Preparation of4-benzyloxy-1-cyclopropylmethyl-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P3.8)

To a solution of4-benzyloxy-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P3.4) (1.0 g, 2.46 mmol) in dioxane (40 ml) was addedbromomethyl-cyclopropane (1.257 ml, 1.78 g, 13.16 mmol) and potassiumtert-butoxide (1.50 g, 13.37 mmol). The reaction mixture was stirred at100° C. for 5 days, then poured on water and extracted with ethylacetate. The combined organic phases were washed with brine, dried oversodium sulfate and concentrated. The residue was suspended in ethylacetate/heptane 1:5, stirred overnight, filtered and dried to afford afirst crop of product as a white solid (350 mg). The mother liquor wasconcentrated, and the residue purified by chromatography on silica gel(dichloromethane/acetone 10:1) to further deliver 205 mg of product.Yield: 555 mg of4-benzyloxy-1-cyclopropylmethyl-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P3.8) as a solid, mp 119-121° C.

¹H-NMR (CD₃OD): 0.34 (m, 2H), 0.52 (m, 2H), 1.10 (m, 1H), 1.48 (br m,1H), 1.83 (br m, 1H), 2.11 (br s, 6H), 2.29 (s, 3H), 2.41 (br m, 1H),2.60 (br m, 1H), 3.12 (br m, 1H), 3.23 (m, 2H), 3.24-3.41 (br signals,total 3H), 3.50 (s, 3H), 4.72 (br signal, 2H), 6.91 (s, 2H), 7.06 (m,2H), 7.29 (m, 3H).

LC/MS (ES+): 461 (M+H)⁺

Step 2: Preparation of1-cyclopropylmethyl-4-hydroxy-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(title compound P2.8)

Debenzylation was conducted using an H-Cube® continuous-flowhydrogenator:4-benzyloxy-1-cyclopropylmethyl-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(546 mg, 1.34 mmol) was dissolved in methanol (47 ml) and this substratesolution (0.029 M) pumped twice through a 5% Pd/C filled cartridge at aflow-rate of 1 mL/min, a temperature of 35° C. and a pressure of 2-3bars. The collected product solution was concentrated, and the residuepurified by chromatography on silica gel (ethyl acetate/heptane 1:1).Yield: 215 mg of1-cyclopropylmethyl-4-hydroxy-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(title compound P2.8) as a white solid, mp 223-225° C.

¹H-NMR (CD₃OD): 0.34 (m, 2H), 0.52 (m, 2H), 1.11 (m, 1H), 1.43 (br m,1H), 1.78 (br m, 1H), 2.11 (s, 6H), 2.25 (s, 3H), 2.41 (br m, 1H), 2.62(br m, 1H), 3.23 (br signal, total 3H), 3.28-3.45 (br signals, total3H), 3.55 (s, 3H), 6.90 (s, 2H).

LC/MS (ES+): 371 (M+H)⁺, 369 (M−H)⁻

Example 4 Preparation of4-Hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P2.2) Step 1: Preparation of1-methoxy-4-methylamino-piperidine-4-carbonitrile (compound P5.1)

To a solution of 1-methoxy-piperidin-4-one [prepared according toJournal of Organic Chemistry (1961), 26, 1867-74] (100 g, 0.77 mol),aqueous methylamine (40 wt. % in H₂O, 86 ml) and methylaminehydrochloride (57.5 g, 0.85 mol) in water (700 ml) at 0° C. was added asolution of potassium cyanide (55.5 g, 0.85 mol) in water (150 ml)dropwise over one hour. The reaction mixture was stirred at roomtemperature for two days. Over the next five days, the mixture wasfurther treated with methylamine hydrochloride (5×2.6 g, total 13.0 g),aqueous methylamine (5×4.3 ml, total 21.5 ml) and potassium cyanide(5×2.5 g, total 12.5 g), and stirring continued at room temperatureuntil the reaction was judged complete by thin layer chromatography. Theaqueous reaction mixture was extracted with dichloromethane (1×500 ml,and 4×200 ml), the combined organic phases dried over sodium sulfate andevaporated. Yield: 113.0 g of1-methoxy-4-methylamino-piperidine-4-carbonitrile (compound P5.1) as ared liquid. This material was used without further purification in thenext step.

¹H-NMR (CDCl₃): 1.36 (br s, 1H), 1.62-2.22 (br signals, total 4H), 2.51(s, 3H), 2.63-3.41 (br signals, total 4H), 3.51 (s, 3H).

IR (CN): ν 2220 cm⁻¹. LC/MS (ES+): 170 (M+H)⁺

Step 2: Preparation ofN-(4-cyano-1-methoxy-piperidin-4-yl)-N-methyl-2-(2,4,6-trimethyl-phenyl)-acetamide(compound P4.1)

Method A: To a solution of1-methoxy-4-methylamino-piperidine-4-carbonitrile (20.0 g, 118.2 mmol),triethylamine (24.6 ml, 17.9 g, 177.3 mmol) and 4-dimethylaminopyridine(DMAP, 0.1 g) in tetrahydrofuran (250 ml) at 0-5° C. was added asolution of (2,4,6-trimethyl-phenyl)-acetyl chloride (25.6 g, 130.0mmol) in THF (25 ml) dropwise over 1.5 hour. The reaction mixture wasstirred at room temperature for a total of three hours, during which itwas further treated with (2,4,6-trimethyl-phenyl)-acetyl chloride (5.4g) and triethylamine (7 ml). The reaction mixture was diluted with ethylacetate and water, the layers separated, the aqueous phase extractedtwice with ethyl acetate, the combined organic phases washed twice withsaturated aqueous sodium hydrogen carbonate and brine, dried over sodiumsulfate and concentrated. The solid residue was suspended in diethylether (500 ml), stirred overnight at room temperature, filtered anddried. Yield: 27.5 g ofN-(4-cyano-1-methoxy-piperidin-4-yl)-N-methyl-2-(2,4,6-trimethyl-phenyl)-acetamide(compound P4.1) as a white solid, mp 171-178° C. This material was usedwithout further purification in the next step.

¹H-NMR (CDCl₃): 2.01 (br m, 1H), 2.11 (br m, 1H), 2.20 (s, 6H), 2.25 (s,3H), 2.34 (br m, 1H), 2.57 (br m, 1H), 2.83 (br m, 1H), 3.12 (s, 3H),3.20 (br m, 1H), 3.34 (br m, 2H), 3.50 (br s, 3H), 3.66 (s, 2H), 6.85(s, 2H).

IR (CN): ν 2231 cm⁻¹. LC/MS (ES+): 330 (M+H)⁺

Method B: To a solution of1-methoxy-4-methylamino-piperidine-4-carbonitrile (20.0 g, 118.2 mmol)in pyridine (250 ml) was added (2,4,6-trimethyl-phenyl)-acetyl chloride(25.6 g, 130.0 mmol) dropwise at 0° C. The reaction mixture was stirredat 0° C. for one hour and at room temperature overnight, poured on icewater and acidified to pH 7 with an aqueous 2N HCl solution. Theresulting thick precipitate was filtered, washed with cold water,dissolved in dichloromethane, dried over sodium sulfate andconcentrated. The solid residue was suspended in hexane, stirred at roomtemperature, filtered and dried. Yield: 32.7 g ofN-(4-cyano-1-methoxy-piperidin-4-yl)-N-methyl-2-(2,4,6-trimethyl-phenyl)-acetamide(compound P4.1) as a pale yellow solid, mp 175-177° C. The spectral dataof this material were identical to those described above underpreparation example 4, step 2, Method A.

Step 3: Preparation of1-methoxy-4-{methyl-[2-(2,4,6-trimethyl-phenyl)-acetyl]-amino}-piperidine-4-carboxylicacid methyl ester (compound P4.2)

To a suspension ofN-(4-cyano-1-methoxy-piperidin-4-yl)-N-methyl-2-(2,4,6-trimethyl-phenyl)-acetamide(106.0 g, 0.322 mol) in methanol (222 ml) at 15-20° C. was addedconcentrated sulfuric acid (85.7 ml, 157.8 g, 1.609 mol) dropwise over75 minutes and the reaction mixture was stirred at room temperature forone hour. The mixture was poured on ice (1 kg), stirred for one hour,then neutralised carefully with 30% aqueous sodium hydroxide to pH 5-5.5(external ice cooling). The thick pasty mixture was diluted with water(1000 ml) and filtered. The solid residue was washed with water andhexane, air-dried and further dried over phosphorus pentoxide undervacuum at 40° C. for two hours. In order to eliminate inorganicimpurities (sodium sulfate!), the solid material was diluted withdichloromethane (600 ml), washed with water (2×300 ml), the aqueousphases extracted once with dichloromethane, the combined organic phasesdried over sodium sulfate and evaporated. Yield: 85.4 g of1-methoxy-4-{methyl-[2-(2,4,6-trimethyl-phenyl)-acetyl]-amino}-piperidine-4-carboxylicacid methyl ester (compound P4.2) as a white solid, mp 133-135° C.

¹H-NMR (CDCl₃): 1.92 (br m, 1H), 2.04 (br m, 1H), 2.16 (s, 6H), 2.23 (s,3H), 2.27-2.49 (br m, 2H), 2.82 (br m, 2H), 3.14 (br m, 2H), 3.22 (br s,3H), 3.52 (s, 3H), 3.62 (br s, 5H), 6.82 (s, 2H).

LC/MS (ES+): 363 (M+H)⁺

Step 4: Preparation of4-hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(title compound P2.2)

To a solution of1-methoxy-4-{methyl-[2-(2,4,6-trimethyl-phenyl)-acetyl]-amino}-piperidine-4-carboxylicacid methyl ester (85.0 g, 234.5 mmol) in dimethylformamide (800 ml) at0° C. was added sodium methoxide (38.0 g, 703.5 mmol) in four portionsand stirring continued at 0° C. for 30 minutes, then at room temperaturefor 1 hour. The reaction mixture was poured on ice and saturated aqueousammonium chloride, acidified to pH 5-6 with concentrated HCl andthoroughly extracted with ethyl acetate. The combined organic layerswere washed with water and brine, dried over sodium sulfate,concentrated and the residue dried in vacuo. Yield: 72.7 g of4-hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(title compound P2.2) as a solid.

The spectral data of this crude material were identical to thosedescribed above under preparation example 1.

Example 5 Preparation of4-Cyclopropylamino-1-methoxy-piperidine-4-carbonitrile (compound P5.2)

To a solution of cyclopropylamine (1.4 ml, 1.14 g, 20.0 mmol) inmethanol (20 ml) at 0° C. was added 1N hydrochloric acid (20 ml, 20.0mmol) dropwise and the mixture was stirred at room temperature for 30minutes. 1-Methoxy-piperidin-4-one [prepared according to Journal ofOrganic Chemistry (1961), 26, 1867-74] (2.58 g, 20.0 mmol), followed 10minutes later by potassium cyanide (1.3 g, 20.0 mmol) in water (10 ml)were then added dropwise at 0° C. The reaction mixture was warmed toroom temperature and stirred overnight, diluted with water and diethylether, the layers separated and the aqueous phase thoroughly extractedwith diethyl ether. The combined organic layers were washed with brine,dried over sodium sulfate and evaporated. Yield: 3.19 g of4-cyclopropylamino-1-methoxy-piperidine-4-carbonitrile (title compoundP5.2) as an oil. This material was used without further purification inthe next step.

¹H-NMR (CDCl₃): 0.42 (br m, 2H), 0.56 (m, 2H), 1.57-2.30 (br signals,total 5H), 2.31 (m, 1H), 2.63-3.41 (br signals, total 4H), 3.51 (br s,3H).

IR (CN): ν 2223 cm⁻¹. LC/MS (ES+): 196 (M+H)⁺

Example 6 Preparation of 1-Methoxy-4-methylamino-piperidine-4-carboxylicacid methyl ester (compound P5.4) Step 1: Preparation of8-methoxy-1-methyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione (compoundP5.6)

To a solution of 1-methoxy-4-methylamino-piperidine-4-carbonitrile(compound P5.1) (10.0 g, 59.09 mmol) in dichloromethane (180 ml) wasadded chlorosulfonyl isocyanate (5.14 ml, 8.36 g, 59.05 mmol) dropwiseover 15 minutes at 20-30° C. The yellowish suspension was stirred atroom temperature for 30 minutes and concentrated to generate a paleyellow solid. This material was dissolved in aqueous 1N hydrochloricacid (180 ml), heated at reflux for one hour, cooled to 0° C. andacidified to pH 5.5 with an aqueous 4N NaOH solution. The aqueous phasewas extracted with ethyl acetate (4×), the combined organic layers werewashed with brine, dried over sodium sulfate and concentrated. Theresidue was purified by chromatography on silica gel (ethylacetate/heptane 1:1). Yield: 3.86 g of8-methoxy-1-methyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione (compoundP5.6) as a solid.

¹H-NMR (CDCl₃): 1.33-2.41 (br signals, total 4H), 2.86 (br s, 3H),3.09-3.42 (br signals, total 4H), 3.52 (br s, 3H), 7.76 (br s, 1H).

LC/MS (ES+): 214 (M+H)⁺

Step 2: Preparation of 1-methoxy-4-methylamino-piperidine-4-carboxylicacid methyl ester (title compound P5.4)

To a suspension of8-methoxy-1-methyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione (3.36 g,15.76 mmol) in water (100 ml) was added sodium hydroxide (0.63 g, 15.75mmol) and the mixture was heated in a microwave apparatus at 190° C. for30 minutes, at 200° C. for one hour and further at 210° C. for one houruntil judged complete by LC-MS analysis. The reaction mixture wasacidified to pH 3 (ice cooling) with an aqueous HCl solution,concentrated in vacuo, the solid residue taken up in warm methanol (40°C.), filtered and the filtrate evaporated. The residue was dried overphosphorus pentoxide at 40° C. overnight. Yield: 2.08 g of1-methoxy-4-methylamino-piperidine-4-carboxylic acid hydrochloride salt.

LC/MS (ES+): 189 (M+H)⁺ of the free base.

To a suspension of 1-methoxy-4-methylamino-piperidine-4-carboxylic acidhydrochloride salt (2.08 g, 9.26 mmol) in methanol (20 ml) at 0-5° C.was added thionyl chloride (2.41 ml, 3.97 g, 33.40 mmol) and thereaction mixture was heated at reflux for 7 days. After cooling, themixture was concentrated, the residue diluted with ice water andneutralised with aqueous sodium bicarbonate. The aqueous phase wasextracted with ethyl acetate (4×), the combined organic layers washedwith brine, dried over sodium sulfate and concentrated. The residue waspurified by chromatography on silica gel (gradient ethyl acetate→ethylacetate/methanol 20:1). Yield: 76 mg of1-methoxy-4-methylamino-piperidine-4-carboxylic acid methyl ester (titlecompound P5.4) as an oil.

¹H-NMR (CDCl₃): 1.46-2.33 (br signals, total 5H), 2.22 (br s, 3H),2.51-3.31 (br signals, total 4H), 3.51 (s, 3H), 3.72 (br s, 3H).

IR (COOMe): ν 1726 cm⁻¹. LC/MS (ES+): 203 (M+H)⁺

Example 7 Preparation of3-(2-Chloro-4,5-dimethyl-phenyl)-4-hydroxy-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P2.26)

To a solution of2-(2-chloro-4,5-dimethyl-phenyl)-N-(4-cyano-1-methoxy-piperidin-4-yl)-N-methyl-acetamide(compound P4.27) (1.15 g, 3.29 mmol) in methanol (˜3 ml) at 10° C. wasadded concentrated sulfuric acid (0.876 ml, 16.43 mmol) dropwise and thereaction mixture was stirred at room temperature overnight. Afterfurther treatment with concentrated sulfuric acid (0.876 ml, 16.43 mmol)and stirring at 80° C. overnight, additional concentrated sulfuric acid(0.876 ml, 16.43 mmol) was added and stirring continued at 90° C. overanother night. The mixture was poured on ice, neutralised carefully with30% aqueous sodium hydroxide to pH 5-6, the resulting precipitatefiltered and dried to afford a first crop of product as a beige solid(225 mg). The mother liquor was concentrated, and the residue purifiedby chromatography on silica gel (ethyl acetate) to further deliver 462mg of product as a yellowish solid. Yield: 687 mg of3-(2-chloro-4,5-dimethyl-phenyl)-4-hydroxy-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]dec-3-en-2-one(title compound P2.26) as a solid, mp 191-192° C.

¹H-NMR (CD₃Cl₃): 1.49-2.57 (br signals, total 4H), 2.20 (s, 3H), 2.21(s, 3H), 2.79-3.46 (br signals, total 4H), 3.00 (br s, 3H), 3.52 (br s,3H), 4.40 (br s, 1H), 6.87 (s, 1H), 7.16 (s, 1H).

LC/MS (ES+): 351/353 (M+H)±

Example 8 Alternative preparation of4-Hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P2.2)

To a solution of4-hydroxy-8-methoxy-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one[starting material (SM) prepared according to WO09/049851] (500 mg, 1.58mmol) in tetrahydrofuran (20 ml) at 0° C. was added a 1.0 M lithiumbis(trimethylsilyl)amide solution in hexanes (3.32 ml, 3.32 mmol)dropwise over 15 minutes. The mixture was stirred one hour at 0° C.,treated with methyl iodide (0.099 ml, 225 mg, 1.59 mmol) dropwise over10 minutes, and further stirred at 0° C. for 30 minutes and at roomtemperature for one hour. The reaction mixture was quenched over coldsaturated aqueous ammonium chloride and extracted with tert-butyl methylether (3×), the combined organic phases washed with brine, dried oversodium sulfate and concentrated. The residue (210 mg) was suspended inhexane, stirred at room temperature for 10 minutes, filtered and dried.Yield: 171 mg of a clean mixture of starting material (SM) and4-hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(title compound P2.2) as a beige solid. ¹H-NMR and LC-MS analysis of thecrude material indicated a ˜1:2.5 ratio of this mixture SM/compoundP2.2.

¹H-NMR (CD₃OD, selected signals only): 6.86 (s, 2H, H_(arom) SM), 6.89(s, 2H, H_(arom) compound P2.2); both signals in a ratio 1:2.6.

LC/MS (ES+): 317 (M+H)⁺; R_(t)=1.40 min for SM. LC/MS (ES+): 331 (M+H)⁺;R_(t)=1.46 min for compound P2.2. Both signals in a ratio 1:2.5considering UV peak areas at 220 nm.

Example 9 Preparation of4-{[2-(2,5-Dimethyl-phenyl)-acetyl]-methyl-amino}-1-methoxy-piperidine-4-carboxylicacid methyl ester (compound P4.46) Step 1: Preparation of1-methoxy-4-methylamino-piperidine-4-carboxylic acid (compound P5.7)

1-Methoxy-4-methylamino-piperidine-4-carbonitrile (compound P5.1) (3.0g, 17.73 mmol) was added in two portions to concentrated sulfuric acid(30 ml) at 0° C. After stirring for 20 minutes, a yellow solution wasobtained which was kept at room temperature overnight. The reactionmixture was carefully diluted with ice water (60 ml), heated at refluxfor 4 hours, then poured on ice (50 g) and neutralised with 25% aqueousammonia under cooling to pH 7-8. The reaction mixture was evaporated andthe white solid residue triturated with warm (40° C.) methanol (3×50ml), filtered and the combined methanol phases concentrated. The residuewas treated with toluene (3×50 ml) to remove water azeotropically untilconstant weight, then triturated with tetrahydrofuran, filtered anddried. Yield: 2.30 g of 1-methoxy-4-methylamino-piperidine-4-carboxylicacid (compound P5.7) as a white solid, mp>250° C.

¹H-NMR (D₂O): 1.73 (m, 1H), 2.02 (m, 2H), 2.32 (m, 1H), 2.54 (appar. d,3H), 2.69 (m, 1H), 2.99 (m, 1H), 3.18 (m, 1H), 3.33 (m, 1H), 3.49(appar. d, 3H). The spectral data are suggesting two major conformers ina 1:1 ratio.

LC/MS (ES+): 189 (M+H)⁺

Step 2: Preparation of 1-methoxy-4-methylamino-piperidine-4-carboxylicacid methyl ester (compound P5.4)

To a suspension of 1-methoxy-4-methylamino-piperidine-4-carboxylic acid(2.0 g, 10.63 mmol) in methanol (50 ml) at 0-10° C. was added thionylchloride (2.29 ml, 3.76 g, 31.57 mmol) and the reaction mixture washeated at reflux overnight. After cooling, the mixture was concentrated,the residue diluted with ice water (20 ml) and neutralised with aqueoussodium bicarbonate. The aqueous phase was extracted with ethyl acetate(4×25 ml) and dichloromethane (4×50 ml), the combined organic layerswashed with aqueous sodium bicarbonate (15 ml) and brine (15 ml), driedover sodium sulfate and concentrated. Yield: 0.76 g of1-methoxy-4-methylamino-piperidine-4-carboxylic acid methyl ester(compound P5.4) as a viscous, orange oil. The spectral data of thiscrude material were identical to those described above under preparationexample 6, step 2.

LC/MS (ES+): 203 (M+H)⁺

Step 3: Preparation of4-{[2-(2,5-dimethyl-phenyl)-acetyl]-methyl-amino}-1-methoxy-piperidine-4-carboxylicacid methyl ester (title compound P4.46)

To a solution of 1-methoxy-4-methylamino-piperidine-4-carboxylic acidmethyl ester (200 mg, 0.99 mmol) in pyridine (5 ml) was added(2,5-dimethyl-phenyl)-acetyl chloride (240 mg, 1.31 mmol) dropwise at 0°C. The reaction mixture was stirred at 0° C. for one hour and at roomtemperature for 6 hours, poured on ice water, acidified to pH 7 with anaqueous 2N HCl solution and diluted with ethyl acetate (50 ml). Thelayers were separated, the aqueous phase extracted with ethyl acetate(3×25 ml), the combined organic phases washed with water (3×15 ml) andbrine, dried over sodium sulfate and concentrated. The residue waspurified by chromatography on silica gel (cyclohexane/ethyl acetate2:1). Yield: 170 mg of4-{[2-(2,5-dimethyl-phenyl)-acetyl]-methyl-amino}-1-methoxy-piperidine-4-carboxylicacid methyl ester (title compound P4.46) as a colorless gum.

¹H-NMR (CD₃OD): 1.99 (br m, 2H), 2.17 (s, 3H), 2.26 (s, 3H), 2.36 (br m,2H), 2.79 (br m, 1H), 2.93 (br m, 1H), 3.06 (appar. d, 3H), 3.21 (br m,2H), 3.50 (s, 3H), 3.67 (s, 3H), 3.68 (br s, 2H), 6.91 (br s, 1H), 6.95(d, 1H), 7.04 (d, 1H).

LC/MS (ES+): 349 (M+H)⁺

Example 10 Preparation of3-Chloro-3-(2-chloro-4,5-dimethyl-phenyl)-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]decane-2,4-dione(compound P1.1)

To a solution of3-(2-chloro-4,5-dimethyl-phenyl)-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]decane-2,4-dione(compound P2.26) (120 mg, 0.342 mmol) and sodium hydrogen carbonate (72mg, 0.857 mmol) in dichloromethane (5 ml) at −5° C. was added sulfurylchloride (0.026 ml, 43.3 mg, 0.321 mmol) in dichloromethane (0.5 ml)dropwise. The reaction mixture was stirred at 0° C. for 1.5 hour, pouredon saturated aqueous sodium carbonate, the layers were separated, thewater phase extracted with ethyl acetate (3×20 ml), the combined organicphases washed with saturated aqueous sodium carbonate and brine, driedover sodium sulfate and concentrated. The residue was purified bychromatography on silica gel (ethyl acetate). Yield: 120 mg of3-chloro-3-(2-chloro-4,5-dimethyl-phenyl)-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]decane-2,4-dione(title compound P1.1) as a white solid, mp 93-94° C.

¹H-NMR (CDCl₃): 1.75-2.71 (br signals, total 4H), 2.24 (s, 3H), 2.29 (s,3H), 2.82-3.46 (br signals, total 4H), 3.04 (br s, 3H), 3.54 (br s, 3H),7.12 (s, 1H), 7.69 (s, 1H).

LC/MS (ES+): 385/387 (M+H)⁺

Example 11 Preparation of3-Chloro-3-(2,5-dimethyl-phenyl)-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]decane-2,4-dione(compound P1.5)

To a solution of3-(2,5-dimethyl-phenyl)-4-hydroxy-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P2.1) (35 mg, 0.111 mmol) and sodium hydrogen carbonate (23mg, 0.274 mmol) in chloroform (5 ml) at −5° C. was added sulfurylchloride (0.009 ml, 15.0 mg, 0.111 mmol) in chloroform (0.25 ml)dropwise. The reaction mixture was stirred at 0° C. for 30 minutes andat room temperature overnight, poured on saturated aqueous sodiumcarbonate, the layers separated, the water phase extracted with ethylacetate (3×20 ml), the combined organic phases washed with saturatedaqueous sodium carbonate and brine, dried over sodium sulfate andconcentrated. The residue was purified by chromatography on silica gel(ethyl acetate/cyclohexane 2:1). Yield: 26 mg of3-chloro-3-(2,5-dimethyl-phenyl)-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]decane-2,4-dione(title compound P1.5) as a pale yellow gum.

¹H-NMR (400 MHz, CDCl₃, selected signals only): δ 2.21 (s, 3H), 2.35 (s,3H), 3.06 (br s, 3H), 3.53 (br s, 3H), 7.04 (d, J=7.8 Hz, 1H), 7.10 (d,J=7.8 Hz, 1H), 7.52 (s, 1H).

LC/MS (ES+): 351/353 (M+H)⁺

Example 12 Preparation of8-Methoxy-1-methyl-3-nitro-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]decane-2,4-dione(compound P1.13)

To a solution of4-hydroxy-8-methoxy-1-methyl-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P2.2) (150 mg, 0.454 mmol) in chloroform (5 ml) at −5° C. wasadded fuming nitric acid (0.038 ml, 57.8 mg, 0.917 mmol) in chloroform(0.5 ml) dropwise. The reaction mixture was stirred at 0° C. for 30minutes and at room temperature for three days, poured on ice water (10ml), the layers were separated, the water phase extracted with ethylacetate (3×20 ml), the combined organic phases washed with water (15 ml)and brine (15 ml), dried over sodium sulfate and concentrated. Theresidue was purified by chromatography on silica gel (ethylacetate/cyclohexane 1:3). Yield: 90 mg of8-methoxy-1-methyl-3-nitro-3-(2,4,6-trimethyl-phenyl)-1,8-diaza-spiro[4.5]decane-2,4-dione(title compound P1.13) as a white solid, mp 127-129° C.

¹H-NMR (400 MHz, CD₃OD, selected signals only): δ 2.24 (s, 6H), 2.26 (s,3H), 3.09 (br s, 3H), 3.52 (br s, 3H), 6.95 (s, 2H).

LC/MS (ES+): 330 (M-NO₂+H)⁺

Example 13 Preparation of3-Chloro-3-(3,4′-dichloro-5-methyl-biphenyl-4-yl)-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]decane-2,4-dione(compound P1.9) Step 1: Preparation of3-(3,4′-Dichloro-5-methyl-biphenyl-4-yl)-4-hydroxy-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]dec-3-en-2-one

To a solution of3-(4-bromo-2-chloro-6-methyl-phenyl)-4-hydroxy-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]dec-3-en-2-one(compound P2.34) (150 mg, 0.361 mmol) in dimethoxyethane (10 ml) underargon atmosphere was added tetrakis(triphenyl-phosphine)palladium(0) (25mg, 0.022 mmol) and the mixture stirred at room temperature for 15minutes. After further addition of water (2 ml), 4-chlorophenylboronicacid (68 mg, 0.435 mmol) and sodium carbonate (153 mg, 1.444 mmol), themixture was heated at 80° C. for 10 hours. The reaction mixture wasacidified at room temperature to pH 4 with 1N hydrochloric acid andextracted with ethyl acetate (4×15 ml). The combined organic layers werewashed with brine, dried over sodium sulfate and concentrated. Theresidue was triturated with diethyl ether, stirred at room temperature,filtered and dried. Yield: 114 mg of3-(3,4′-dichloro-5-methyl-biphenyl-4-yl)-4-hydroxy-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]dec-3-en-2-oneas a pale brown solid, mp 236° C. (dec).

¹H-NMR (400 MHz, CD₃OD, selected signals only): δ 2.28 (s, 3H), 2.90 (brs, 3H), 3.56 (s, 3H), 7.36 (d, J=8.3 Hz, 1H), 7.46 (m, 2H), 7.57 (d,J=8.3 Hz, 1H), 7.62 (m, 2H).

LC/MS (ES+): 447/449 (M+H)⁺

Step 2: Preparation of3-Chloro-3-(3,4′-dichloro-5-methyl-biphenyl-4-yl)-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]decane-2,4-dione(title compound P1.9)

To a solution of3-(3,4′-dichloro-5-methyl-biphenyl-4-yl)-4-hydroxy-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]dec-3-en-2-one(100 mg, 0.224 mmol) and sodium hydrogen carbonate (47 mg, 0.560 mmol)in dichloromethane (5 ml) at −5° C. was added sulfuryl chloride (0.017ml, 28.3 mg, 0.210 mmol) in dichloromethane (0.5 ml) dropwise. Thereaction mixture was stirred at 0° C. for 30 minutes and at roomtemperature overnight, poured on saturated aqueous sodium carbonate, thelayers were separated, the water phase extracted with ethyl acetate(3×20 ml), the combined organic phases washed with saturated aqueoussodium carbonate and brine, dried over sodium sulfate and concentrated.The residue was purified by chromatography on silica gel (ethylacetate/cyclohexane 2:1). Yield: 65 mg of3-chloro-3-(3,4′-dichloro-5-methyl-biphenyl-4-yl)-8-methoxy-1-methyl-1,8-diaza-spiro[4.5]decane-2,4-dione(title compound P1.9) as a gum.

¹H-NMR (400 MHz, CDCl₃, selected signals only): δ 2.86 (s, 3H), 3.04 (brs, 3H), 3.54 (br s, 3H), 7.36 (m, 2H), 7.41 (m, 2H), 7.46 (m, 2H).

LC/MS (ES+): 481/483/485 (M+H)⁺

Compounds of the formula I from Table P1, compounds of the formula IIfrom Table P2 and intermediates listed in Tables P3, P4 and P5 can beprepared by analogous procedures. Either one of the following LC-MSmethods was used to characterize the compounds:

Method A

MS: ZQ Mass Spectrometer from Waters (Single quadrupole massspectrometer); Ionisation method: Electrospray; Polarity:positive/negative ions; Capillary (kV) 3.00, Cone (V) 30.00, Extractor(V) 2.00, Source Temperature (° C.) 100, Desolvation Temperature (° C.)250, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 400; Massrange: 150 to 1000 or 100 to 900 Da.

LC: HP 1100 HPLC from Agilent: solvent degasser, quaternary pump(ZCQ)/binary pump (ZDQ), heated column compartment and diode-arraydetector. Column: Phenomenex Gemini C18, 3 μm particle size, 110AngstrOm, 30×3 mm, Temp: 60° C.; DAD Wavelength range (nm): 200 to 500;Solvent gradient: A=water+0.05% v/v HCOOH, B=Acetonitril/Methanol (4:1,v/v)+0.04% v/v HCOOH.

Time (min) A % B % Flow (ml/min) 0.00 95.0 5.0 1.700 2.00 0.0 100.01.700 2.80 0.0 100.0 1.700 2.90 95.0 5.0 1.700 3.00 95.0 5.0 1.700Method B

MS: ZMD Mass Spectrometer from Waters (Single quadrupole massspectrometer); Ionisation method: Electrospray; Polarity:positive/negative ions; Capillary (kV) 3.80, Cone (V) 30.00, Extractor(V) 3.00, Source Temperature (° C.) 150, Desolvation Temperature (° C.)350, Cone Gas Flow (L/Hr) OFF, Desolvation Gas Flow (L/Hr) 600; Massrange: 150 to 1000 (100 to 1500 for LowMass) or 100 to 900 Da.

LC: HP 1100 HPLC from Agilent: solvent degasser, binary pump, heatedcolumn compartment and diode-array detector. Column: Phenomenex GeminiC18, 3 μm particle size, 110 Angstöm, 30×3 mm, Temp: 60° C.; DADWavelength range (nm): 200 to 500; Solvent gradient: A=water+0.05% v/vHCOOH, B=Acetonitril/Methanol (4:1, v:v)+0.04% v/v HCOOH.

Time (min) A % B % Flow (ml/min) 0.00 95.0 5.0 1.700 2.00 0.0 100.01.700 2.80 0.0 100.0 1.700 2.90 95.0 5.0 1.700 3.00 95.0 5.0 1.700Method C

MS: ZQ Mass Spectrometer from Waters (Single quadrupole massspectrometer); Ionisation method: Electrospray; Polarity:positive/negative ions; Capillary (kV) 3.00, Cone (V) 30.00, Extractor(V) 2.00, Source Temperature (° C.) 100, Desolvation Temperature (° C.)250, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 400; Massrange: 100 to 900 Da.

LC: HP 1100 HPLC from Agilent: solvent degasser, quaternary pump (ZCQ),heated column compartment and diode-array detector. Column: PhenomenexGemini C18, 3 μm particle size, 30×3 mm, Temp: 60° C.; DAD Wavelengthrange (nm): 210 to 500; Solvent gradient: A=water+5% v/v Methanol+0.05%v/v HCOOH, B=Acetonitril+0.05% v/v HCOOH.

Time (min) A % B % Flow (ml/min) 0.00 100 0 1.700 2.00 0 100 1.700 2.800 100 1.700 2.90 100 0 1.700 3.00 100 0 1.700

The characteristic values obtained for each compound were the retentiontime (“R_(t)”, recorded in minutes) and the molecular ion as listed inTable P1, Table P2, Table P3, Table P4 and in Table P5.

TABLE P1 Physical data of compounds of formula I: Compound Melting No.Structures Point MS/NMR P1.1

93-94° C. LC/MS: 385/387 (M + H)⁺ R_(t) = 1.81 min EXAMPLE 10 P1.2

69-71° C. LC/MS: 429/431/433 (M + H)⁺ R_(t) = 1.90 min P1.3

88-90° C. LC/MS: 429/431/433 (M + H)⁺ R_(t) = 1.92 min P1.4

gum LC/MS: 365/367 (M + H)⁺ R_(t) = 1.87 min P1.5

gum LC/MS: 351/353 (M + H)⁺ R_(t) = 1.73 min EXAMPLE 11 P1.6

gum LC/MS: 405/407 (M + H)⁺ R_(t) = 2.01 min P1.7

112-113° C. LC/MS: 351/353 (M + H)⁺ R_(t) = 1.72 min P1.8

gum LC/MS: 435/437 (M + H)⁺ R_(t) = 1.94 min P1.9

gum LC/MS: 481/483/485 (M + H)⁺ R_(t) = 2.08 min EXAMPLE 13  P1.10

115-117° C. LC/MS: 401/403 (M + H)⁺ R_(t) = 1.77 min  P1.11

106-108° C. LC/MS: 399/401 (M + H)⁺ R_(t) = 1.93 min  P1.12

gum LC/MS: 461/463 (M + H)⁺ R_(t) = 2.08 min  P1.13

127-129° C. LC/MS: 330 (M—NO₂ + H)⁺ R_(t) = 1.84 min EXAMPLE 12  P1.14

gum LC/MS: 429/431 (M + H)⁺ R_(t) = 1.93 min  P1.15

gum LC/MS: 461/463 (M + H)⁺ R_(t) = 2.13 min  P1.16

solid LC/MS: 427/429 (M + H)⁺ R_(t) = 1.99 min

TABLE P2 Physical data of compounds of formula II: Compound Melting No.Structures Point MS/NMR P2.1 

121-123° C. LC/MS: 317 (M + H)⁺ R_(t) = 1.49 min P2.2 

241-243° C. LC/MS: 331 (M + H)⁺ R_(t) = 1.44 min EXAMPLE 1 EXAMPLE 2,step 3 EXAMPLE 4, step 4 P2.3 

solid ¹H-NMR (400 MHz, CDCl₃): 1.75 (m, 2H), 2.31 (m, 2H), 2.48 (m, 2H),3.47 (m, 2H), 3.58 (s, 3H), 3.93 (m, 2H), 5.90 (m, 1H), 6.30 (br s, 1H),7.25-7.32 (m, 2H), 7.40 (m, 1H). P2.4 

solid ¹H-NMR (400 MHz, CDCl₃, selected signals only): 3.57 (s, 3H,NOCH₃), 5.85 (m, 1H, CHF₂), 6.52 (br s, 1H), 7.27-7.35 (m, 2H,H_(arom)), 7.49 (d, 1H, H_(arom)) P2.5 

solid ¹H-NMR (400 MHz, CDCl₃, selected signals only): 2.18 (s, 3H,phenyl CH₃), 2.31 (s, 3H, phenyl CH3), 3.39 (s, 3H, NOCH₃), 5.78 (m, 1H,CHF₂), 6.19 (br s, 1H), 7.00 (s, 1H, H_(arom)), 7.08 (d, 1H, H_(arom)),7.12 (d, 1H, H_(arom)). P2.6 

205-207° C. LC/MS: 361 (M + H)⁺ R_(t) = 1.47 min P2.7 

solid LC/MS: 375 (M + H)⁺ R_(t) = 1.58 min P2.8 

223-225° C. LC/MS: 371 (M + H)⁺ R_(t) = 1.76 min EXAMPLE 3, step 2 P2.9 

>240° C. LC/MS: 351/353 (M + H)⁺ R_(t) = 1.48 min P2.10

208-211° C. LC/MS: 357 (M + H)⁺ R_(t) = 1.61 min P2.11

218-221° C. LC/MS: 345 (M + H)⁺ R_(t) = 1.58 min P2.12

solid LC/MS: 355/357 (M + H)⁺ R_(t) = 1.52 min P2.13

54-57° C. LC/MS: 355/357 (M + H)⁺ R_(t) = 1.49 min P2.14

solid LC/MS: 395/397 (M + H)⁺ R_(t) = 1.48 min P2.15

191-195° C. LC/MS: 351/353 (M + H)⁺ R_(t) = 1.58 min P2.16

234-235° C. LC/MS: 395/397 (M + H)⁺ R_(t) = 1.54 min P2.17

202-204° C. LC/MS: 317 (M + H)⁺ R_(t) = 1.36 min P2.18

gum LC/MS: 399/401 (M + H)⁺ R_(t) = 1.54 min P2.19

80-82° C. ¹H-NMR (CD3OD, selected signals only): 2.12 (s, 6H, mesitylCH₃), 2.27 (s, 3H, mesityl CH₃), 3.37 (s, 3H, CH₂CH₂OCH₃), 3.47 (t, 2H,CH₂CH₂OMe), 3.55 (s, 3H, NOCH₃), 3.65 (t, 2H, CH₂CH₂OMe), 6.91 (s, 2H,H_(arom)) P2.20

79-81° C. LC/MS: 389 (M + H)⁺ R_(t) = 1.62 min P2.21

181-183° C. LC/MS: 405 (M + H)⁺ R_(t) = 1.60 min P2.22

solid LC/MS: 345 (M + H)⁺ R_(t) = 1.55 min P2.23

191-193° C. LC/MS: 395/397 (M + H)⁺ R_(t) = 1.59 min P2.24

192-194° C. LC/MS: 331 (M + H)⁺ R_(t) = 1.41 min P2.25

183-186° C. LC/MS: 331 (M + H)⁺ R_(t) = 1.56 min P2.26

191-192° C. LC/MS: 351/353 (M + H)⁺ R_(t) = 1.60 min EXAMPLE 7 P2.27

138-142° C. LC/MS: 351/353 (M + H)⁺ R_(t) = 1.49 min P2.28

182-183° C. LC/MS: 395/397 (M + H)⁺ R_(t) = 1.62 min P2.29

solid LC/MS: 317 (M + H)⁺ R_(t) = 1.47 min P2.30

180-182° C. LC/MS: 401 (M + H)⁺ R_(t) = 1.50 min P2.31

gum LC/MS: 365/367 (M + H)⁺ R_(t) = 1.59 min P2.32

211-213° C. LC/MS: 401 (M + H)⁺ R_(t) = 1.60 min P2.33

solid LC/MS: 351/353 (M + H)⁺ R_(t) = 1.50 min P2.34

>200° C. LC/MS: 415/417/419 (M + H)⁺ R_(t) = 1.54 min

Intermediates of the formula XIII or XIV from Table P3 can be preparedby analogous procedures.

TABLE P3 Physical data of intermediates of formula XIII or XIV: CompoundMelting No. Structures Point MS/NMR P3.1

128-131° C. Described in WO09/049851 P3.2

180-183° C. Described in WO09/049851 P3.3

111-113° C. Described in WO09/049851 P3.4

184-186° C. LC/MS: 407 (M + H)⁺ R_(t) = 2.02 min P3.5

139-141° C. LC/MS: 421 (M + H)⁺ R_(t) = 2.04 min P3.6

solid LC/MS: 451 (M + H)⁺ R_(t) = 2.08 min P3.7

solid LC/MS: 465 (M + H)⁺ R_(t) = 2.05 min P3.8

119-121° C. LC/MS: 461 (M + H)⁺ R_(t) = 2.19 min P3.9

134-136° C. LC/MS: 447 (M + H)⁺ R_(t) = 2.14 min  P3.10

solid LC/MS: 435 (M + H)⁺ R_(t) = 2.07 min  P3.11

90-92° C. LC/MS: 495 (M + H)⁺ R_(t) = 2.06 min  P3.12

68-70° C. LC/MS: 495 (M + H)⁺ R_(t) = 2.05 min  P3.13

solid LC/MS: 479 (M + H)⁺ R_(t) = 2.07 min  P3.14

LC/MS: 491 (M + H)⁺ R_(t) = 2.04 min

Intermediates of the formula IV or XI from Table P4 can be prepared byanalogous procedures.

TABLE P4 Physical data of intermediates of formula IV or XI: CompoundMelting No. Structures Point MS/NMR P4.1 

175-177° C. LC/MS: 330 (M + H)⁺ R_(t) = 1.78 min P4.2 

133-135° C. LC/MS: 363 (M + H)⁺ R_(t) = 1.79 min P4.3 

LC/MS: 350/352 (M + H)⁺ R_(t) = 1.78 min P4.4 

LC/MS: 383/385 (M + H)⁺ R_(t) = 1.79 min P4.5 

LC/MS: 354/356 (M + H)⁺ R_(t) = 1.71 min P4.6 

LC/MS: 387/389 (M + H)⁺ R_(t) = 1.73 min P4.7 

LC/MS: 354/356 (M + H)⁺ R_(t) = 1.70 min P4.8 

LC/MS: 387/389 (M + H)⁺ R_(t) = 1.71 min P4.9 

LC/MS: 394/396 (M + H)⁺ R_(t) = 1.78 min P4.10

LC/MS: 427/429 (M + H)⁺ R_(t) = 1.81 min P4.11

LC/MS: 350/352 (M + H)⁺ R_(t) = 1.78 min P4.12

LC/MS: 383/385 (M + H)⁺ R_(t) = 1.78 min P4.13

solid LC/MS: 394/396 (M + H)⁺ R_(t) = 1.78 min P4.14

solid LC/MS: 427/429 (M + H)⁺ R_(t) = 1.80 min P4.15

171-174° C. LC/MS: 316 (M + H)⁺ R_(t) = 1.64 min P4.16

139-141° C. LC/MS: 349 (M + H)⁺ R_(t) = 1.64 min P4.17

gum LC/MS: 398/400 (M + H)⁺ R_(t) = 1.71 min P4.18

solid LC/MS: 431/433 (M + H)⁺ R_(t) = 1.75 min P4.19

¹H-NMR (CDCl₃, selected signals only): 3.15 (s, 3H, N—CH₃), 3.50 (br s,3H, NOCH₃), 3.75 (s, 2H, PhCH₂CO), 6.89 (s, 1H, H_(arom)). P4.20

LC/MS: 377 (M + H)⁺ R_(t) = 1.81 min P4.21

gum LC/MS: 427/429 (M + H)⁺ R_(t) = 1.82 min P4.22

123-126° C. LC/MS: 394/396 (M + H)⁺ R_(t) = 1.82 min P4.23

¹H-NMR (CDCl₃, selected signals only): 2.13 (s, 3H, phenyl CH₃), 2.22(s, 3H, phenyl CH₃), 2.25 (s, 3H, phenyl CH₃), 3.14 (s, 3H, N—CH₃), 3.51(br s, 3H, NOCH₃), 3.73 (s, 2H, PhCH₂CO). P4.24

¹H-NMR (CDCl₃, selected signals only): 3.52 (br s, 3H, NOCH₃). P4.25

LC/MS: 330 (M + H)⁺ R_(t) = 1.78 min P4.26

LC/MS: 363 (M + H)⁺ R_(t) = 1.77 min P4.27

solid LC/MS: 350/352 (M + H)⁺ R_(t) = 1.54 min P4.28

P4.29

P4.30

P4.31

134-136° C. LC/MS: 400 (M + H)⁺ R_(t) = 1.87 min P4.32

132-134° C. LC/MS: 433 (M + H)⁺ R_(t) = 1.87 min P4.33

144-146° C. LC/MS: 394/396 (M + H)⁺ R_(t) = 1.82 min P4.34

gum LC/MS: 427/429 (M + H)⁺ R_(t) = 1.84 min P4.35

solid LC/MS: 316 (M + H)⁺ R_(t) = 1.66 min P4.36

solid LC/MS: 349 (M + H)⁺ R_(t) = 1.67 min P4.37

188-192° C. LC/MS: 350/352 (M + H)⁺ R_(t) = 1.75 min P4.38

150-152° C. LC/MS: 383/385 (M + H)⁺ R_(t) = 1.77 min P4.39

solid LC/MS: 414/416/418 (M + H)⁺ R_(t) = 1.78 min P4.40

gum LC/MS: 447/449/451 (M + H)⁺ R_(t) = 1.82 min P4.41

LC/MS: 356 (M + H)⁺ R_(t) = 1.87 min P4.42

LC/MS: 389 (M + H)⁺ R_(t) = 1.89 min P4.43

gum LC/MS: 370 (M + H)⁺ R_(t) = 1.99 min P4.44

P4.45

P4.46

gum LC/MS: 349 (M + H)⁺ R_(t) = 1.66 min

Intermediates of the formula V, VII, VIII or IX from Table P5 can beprepared by analogous procedures.

TABLE P5 Physical data of intermediates of formula V, VII, VIII or IX:Compound Melting No. Structures Point MS/NMR/IR P5.1

liquid ¹H-NMR (CDCl₃): 1.36 (br s, 1H), 1.62-2.22 (br signals, total4H), 2.51 (s, 3H), 2.63-3.41 (br signals, total 4H), 3.51 (s, 3H). LC/MS(ES+): 170 (M + H)⁺; R_(t) = 0.25 min P5.2

LC/MS: 196 (M + H)⁺ R_(t) = 1.14 min IR (CN): ν 2223 cm⁻¹ P5.3

oil LC/MS: 240 (M + H)⁺ R_(t) = 1.18 min P5.4

oil ¹H-NMR (CDCl₃): 1.46-2.33 (br signals, total 5H), 2.22 (br s, 3H),2.51- 3.31 (br signals, total 4H), 3.51 (s, 3H), 3.72 (br s, 3H). LC/MS(ES+): 203 (M + H)⁺; R_(t) = 0.20 min P5.5

LC/MS: 210 (M + H)⁺ R_(t) = 1.10 min IR (CN): ν 2222 cm⁻¹ P5.6

solid LC/MS: 214 (M + H)⁺ R_(t) = 0.75 min P5.7

>250° C. ¹H-NMR (D₂O): 1.73 (m, 1H), 2.02 (m, 2H), 2.32 (m, 1H), 2.54(appar. d, 3H), 2.69 (m, 1H), 2.99 (m, 1H), 3.18 (m, 1H), 3.33 (m, 1H),3.49 (appar. d, 3H). LC/MS (ES+): 189 (M + H)⁺; R_(t) = 0.21 min

FORMULATION EXAMPLES %=Percent by Weight Example F1 EmulsionConcentrates

a) b) c) Active ingredient 25% 40% 50% Calcium dodecylbenzenesulfonate 5%  8%  6% Castor oil polyethylene glycol ether (36 mol of EO)  5% — —Tributylphenoxypolyethylene glycol ether (30 mol — 12%  4% of EO)Cyclohexanone — 15% 20% Xylene mixture 65% 25% 20%

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

Example F2 Solutions

a) b) c) d) Active ingredient 80% 10% 5% 95% Ethylene glycol monomethylether 20% — — — Polyethylene glycol MW 400 — 70% — —N-Methylpyrrolid-2-one — 20% — — Epoxidized coconut oil — — 1%  5%Petroleum ether (boiling range: 160-190°) — — 94%  —

The solutions are suitable for use in the form of microdrops.

Example F3 Granules

a) b) c) d) Active ingredient 5% 10%  8% 21% Kaolin 94%  — 79% 54%Highly disperse silica 1% — 13%  7% Attapulgite — 90% — 18%

The active ingredient is dissolved in dichloromethane, the solution issprayed onto the carrier(s), and the solvent is subsequently evaporatedin vacuo.

Example F4 Dusts

a) b) Active ingredient 2% 5% Highly disperse silica 1% 5% Talc 97%  —Kaolin — 90% 

Ready-to-use dusts are obtained by intimately mixing the carriers andthe active ingredient.

Example F5 Wettable Powders

a) b) c) Active ingredient 25%  50% 75% Sodium lignosulfonate 5%  5% —Sodium lauryl sulfate 3% —  5% Sodium diisobutylnaphthalenesulfonate — 6% 10% Octylphenoxypolyethylene glycol ether (7-8 mol of EO) —  2% —Highly disperse silica 5% 10% 10% Kaolin 62%  27% —

The active ingredient is mixed with the additives and the mixture isground thoroughly in a suitable mill. This gives wettable powders, whichcan be diluted with water to give suspensions of any desiredconcentration.

Example F6 Extruder Granules

Active ingredient 10% Sodium lignosulfonate 2% Carboxymethylcellulose 1%Kaolin 87%

The active ingredient is mixed with the additives, and the mixture isground, moistened with water, extruded, granulated and dried in a streamof air.

Example F7 Coated Granules

Active ingredient 3% Polyethylene glycol (MW 200) 3% Kaolin 94%

In a mixer, the finely ground active ingredient is applied uniformLy tothe kaolin, which has been moistened with the polyethylene glycol. Thisgives dust-free coated granules.

Example F8a Suspension Concentrate

Active ingredient 40% Ethylene glycol 10% Nonylphenoxypolyethyleneglycol ether (15 mol of EO) 6% Sodium lignosulfonate 10%Carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2%Silicone oil (75% aqueous emulsion) 0.8% Water 32%

Example F8b Suspension Concentrate

Active ingredient 10% Naphthalenesulfonic acid, sodium salt condensedwith 2% formaldehyde Solution of an acrylic graft copolymer in water and8% propyleneglycole Silicone antifoam emulsion 0.5% DL-propanediol-(1,2)3% Heteropolysaccharide 0.5% 1,2-Benzisothiazol-3-one 0.2% Water 75.8%

The finely ground active ingredient is mixed intimately with theadditives. Suspensions of any desired concentration can be prepared fromthe thus resulting suspension concentrate by dilution with water.

Example F9 Powders for Dry Seed Treatment

a) b) c) active ingredient 25% 50% 75% light mineral oil  5%  5%  5%highly dispersed silicic acid  5%  5% — Kaolin 65% 40% — Talcum — 20%

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording powders thatcan be used directly for seed treatment.

Example F10 Flowable Concentrate for Seed Treatment

active ingredient 40% propylene glycol 5% copolymer butanol PO/EO 2%tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (inthe form of a 20% solution in 0.5% water) monoazo-pigment calcium salt5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water45.3%

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Example F11a Oil-Based Suspension Concentrate (Based on a Vegetable Oil)

Active ingredient 10% Tristyrylphenole with 16 moles EO 10% Blockcopolymer of polyhydroxystearic acid and polyalkylene 2% glycols AEROSIL200 1% Rape seed oil methyl ester 12% Oleic acid 65%

Example F11b Oil-Based Suspension Concentrate (Based on a Mineral Oil)

Active ingredient 10% Ethoxylated alcohols, C16-18 and C18-unsatd 5%Dodecyl-benzene sulfonic acid Ca-salt linear 2.5% 2-Pyrrolidinone,1-ethenylhexadecyl-, homopolymer 1% Organophilic clay 1% Mixture ofpetroleum 80.5%

The finely ground active ingredient is mixed intimately with theadditives. Suspensions of any desired concentration can be prepared fromthe thus resulting suspension concentrate by dilution with water.

Preferably, the term “active ingredient” used above refers to one of thecompounds selected from Tables 1 to 155 shown above. It also refers tomixtures of the compound of formula I, in particular a compound selectedfrom said Tables 1 to 155, with other insecticides, fungicides,herbicides, safeners, adjuvants and the like, which mixtures arespecifically disclosed above.

BIOLOGICAL EXAMPLES

These examples illustrate the pesticidal/insecticidal properties ofcompounds of formula I.

Example B1 Activity Against Myzus persicae (Green Peach Aphid) (MixedPopulation, Feeding/Residual Contact Activity, Preventive)

Sunflower leaf discs are placed on agar in a 24-well microtiter plateand sprayed with test solutions. After drying, the leaf discs areinfested with an aphid population of mixed ages. After an incubationperiod of 6 days, samples are checked for mortality and special effects(e.g. phytotoxicity).

In this test, compounds listed in the tables above show good activity.In particular compounds P1.1, P1.2, P1.3, P1.4, P1.11, P1.12, P1.13 andP1.14 show an activity of over 80% at a concentration of 400 ppm.

Example B2 Activity Against Myzus persicae (Green Peach Aphid) (MixedPopulation, Systemic/Feeding Activity, Curative)

Roots of pea seedlings, infested with an aphid population of mixed ages,are placed directly in the test solutions. 6 days after introduction,samples are checked for mortality and special effects on the plant.

In this test, compounds listed in the tables above show good activity.In particular compounds P1.3, P1.4 and P1.7 show an activity of over 80%at a concentration of 400 ppm.

Example B3 Activity Against Thrips tabaci (Onion Thrips) (MixedPopulation, Feeding/Residual Contact Activity, Preventive)

Sunflower leaf discs are placed on agar in a 24-well microtiter plateand sprayed with test solutions. After drying, the leaf discs areinfested with a thrips population of mixed ages. After an incubationperiod of 6 days, samples are checked for mortality and special effects(e.g. phytotoxicity).

In this test, compounds listed in the tables above show good activity.In particular compounds P1.2 and P1.4 show an activity of over 80% at aconcentration of 400 ppm.

Example B4 Activity Against Tetranychus urticae (Two-Spotted SpiderMite) (Mixed Population, Feeding/Residual Contact Activity, Preventive)

Bean leaf discs on agar in 24-well microtiter plates are sprayed withtest solutions. After drying, the leaf discs are infested with mitepopulations of mixed ages. 8 days later, discs are checked for eggmortality, larval mortality, and adult mortality.

In this test, compounds listed in the tables above show good activity.In particular compound P1.1 shows an activity of over 80% at aconcentration of 400 ppm.

Example B5 Activity Against Myzus persicae (Green Peach Aphid) (MixedPopulation, Feeding/Residual Contact Activity, Plant Damage Evaluation)

Cabbage plants infested with a mixed population of Myzus persicae aretreated with diluted test solutions of the compounds in a spray chamber.6 days after treatment, samples are checked for mortality and for plantdamage (phytotoxicity), visual assessment being made using a 0-100%rating scale (100%=total damage to plant; 0%=no damage to plant). Inthis test, compounds listed in the tables above show good activityagainst Myzus persicae and acceptable plant compatibility. For examplecompounds P1.2, P1.3, P1.4, P1.5, P1.6, P1.7, P1.8, P1.11, P1.12, P1.13and P1.14 show an activity of greater or equal to 80% against Myzuspersicae and damage to cabbage plants less or equal to 10% at aconcentration of 200 ppm.

The invention claimed is:
 1. Compounds of the formula I

wherein X, Y and Z independently of each other are C₁₋₄alkyl,C₃₋₆cycloalkyl, C₁₋₄alkoxy, halogen, phenyl or phenyl substituted byC₁₋₄alkyl, C₁₋₄haloalkyl, halogen or cyano; m and n, independently ofeach other, are 0, 1, 2 or 3 and m+n is 0, 1, 2 or 3; G is halogen ornitro; R is hydrogen, C₁₋₆alkyl, C₁₋₆cyanoalkyl, C₂₋₆alkenyl,C₂₋₆haloalkenyl, C₃₋₆alkynyl, benzyl, C₁₋₄alkoxy(C₁₋₄)alkyl, orC₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl; and A is C₁₋₆alkyl, C₃₋₆cycloalkyl,C₃₋₆cycloalkyl(C₁₋₄)alkyl, or C₃₋₆cycloalkyl(C₁₋₄)alkyl where in thecycloalkyl moiety a methylene group is replaced by O, S or NR₀, where R₀is C₁₋₆alkyl or C₁₋₆alkoxy, or A is C₂₋₆alkenyl, C₂₋₆haloalkenyl,C₃₋₆alkynyl, C₁₋₆cyanoalkyl, benzyl, C₁₋₄alkoxy(C₁₋₄)alkyl,C₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl, oxetanyl, tetrahydrofuranyl,tetrahydropyranyl, C₁₋₆alkylcarbonyl, C₁₋₆alkoxycarbonyl,C₃₋₆cycloalkylcarbonyl, N-di(C₁₋₆alkyl)carbamoyl, benzoyl,C₁₋₆alkylsulfonyl, phenylsulfonyl, C₁₋₄alkylthio(C₁₋₄)alkyl,C₁₋₄alkylsulfinyl(C₁₋₄)alkyl or C₁₋₄alkylsulfonyl(C₁₋₄)alkyl; or anagrochemically acceptable salt or an N-oxide thereof.
 2. A process forthe preparation of compounds of the formula I according to claim 1,wherein G is halogen or nitro, which comprises reacting compounds offormula II

wherein X, Y, Z, m, n, A and R have the meanings assigned to them inclaim 1, with halogenating or nitrating agents, in the presence of asolvent and, optionally, in the presence of a base and/or a free-radicalinitiator.
 3. A pesticidal composition comprising a pesticidal effectiveamount of at least one compound of formula I according to claim
 1. 4. Apesticidal composition according to claim 3, which, in addition tocomprising the compound of formula I, comprises formulation adjuvants.5. A pesticidal composition according to claim 3, which, in addition tocomprising the compound of formula I, comprises at least one additionalinsecticide, acaricide, nemacitide or molluscicide.
 6. A pesticidalcomposition according to claim 3, which, in addition to comprising thecompound of formula I, comprises at least one additional fungicide,herbicide, safener or plant growth regulator.
 7. A method of combatingand controlling pests which comprises applying to a pest, to a locus ofa pest, or to a plant susceptible to attack by a pest a pesticidallyeffective amount of a compound of formula I.
 8. A method of combatingand controlling pests which comprises applying to a pest, to a locus ofa pest, or to a plant susceptible to attack by a pest a pesticidalcomposition according to claim 3.